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71.
Miniaturization of analytical instruments has attracted a wide interest in analytical chemistry over the past decade because of the advantages of reduced reagent consumption, better analytical performance, and shorter analysis time. The widespread interest in this field has resulted in efforts to develop chips. For chips involving separation, injection is a key step to achieve efficient and sensitive analysis. This work presents a comparative study of two electrokinetic injection modes in chips: the floating, which has been mainly used up to now, and the dynamic. This study was done with a crossjunction, either with numerical simulations or with experiments. Experiments were carried out with homemade PDMS-glass microsystems involving zonal electrophoresis analysis of five derivatized amino acids. Injected amount, reproducibility, separation efficiency, and analyte discrimination were evaluated and discussed. The experimental results were successfully correlated with numerical simulations. It appeared that the dynamic injection mode is much more appropriate than the floating mode as it is faster (reduction by a factor 2 of the total analysis time here), more reproducible (RSD of peak areas equal to 1.3% (n = 4) instead of 10% (n = 4)), and leads to more efficient separation (about 20% with 3 cm separation channel length) for the same injected amount, whatever the amount, because the sample plug is less dispersed. 相似文献
72.
73.
Petkova V Benattar JJ Zoonens M Zito F Popot JL Polidori A Jasseron S Pucci B 《Langmuir : the ACS journal of surfaces and colloids》2007,23(8):4303-4309
The possibility of organizing detergent-solubilized membrane proteins in a plane within the core of Newton black films (NBFs) formed from fluorinated surfactants has been investigated. Fluorinated surfactants have the interesting characteristics of being poorly miscible with detergents and highly surface-active. As a result, when a membrane protein-the transmembrane domain of OmpA (tOmpA)-solubilized by the nonionic detergent C8E4 (tetraethylene glycol monooctyl ether) was injected under a monolayer of fluorinated surfactant, C8E4 and tOmpA/C8E4 complexes remained confined to the subphase. Vertical, macroscopic NBFs were drawn, and their structure was investigated by means of X-ray reflectivity. Depending on experimental conditions, the protein was shown to organize into either one or two monolayers stabilized by two monolayers of fluorinated surfactant. Two different mechanisms of protein insertion were investigated: (i) attachment of polyhistidine-tagged tOmpA/C8E4 complexes to nickel-bearing polar groups born by a fluorinated surfactant and (ii) spontaneous diffusion into the surfactant films. Possible applications are discussed. 相似文献
74.
We propose in this contribution to investigate the link between the dynamic gradient damage model and the classical Griffith’s theory of dynamic fracture during the crack propagation phase. To achieve this main objective, we first rigorously reformulate two-dimensional linear elastic dynamic fracture problems using variational methods and shape derivative techniques. The classical equation of motion governing a smoothly propagating crack tip follows by considering variations of a space-time action integral. We then give a variationally consistent framework of the dynamic gradient damage model. Owing to the analogies between the variational ingredients of these two models and under some basic assumptions concerning the damage band structuration, one obtains a generalized Griffith criterion which governs the crack tip evolution within the non-local damage model. Assuming further that the internal length is small compared to the dimension of the body, the previous criterion leads to the classical Griffith’s law through a separation of scales between the outer linear elastic domain and the inner damage process zone. 相似文献
75.
Pump−probe experiments at the TEMPO beamline using the low‐α operation mode of Synchrotron SOLEIL
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Mathieu G. Silly Tom Ferté Marie Agnes Tordeux Debora Pierucci Nathan Beaulieu Christian Chauvet Federico Pressacco Fausto Sirotti Horia Popescu Victor Lopez-Flores Marina Tortarolo Maurizio Sacchi Nicolas Jaouen Philippe Hollander Jean Paul Ricaud Nicolas Bergeard Christine Boeglin Bharati Tudu Renaud Delaunay Jan Luning Gregory Malinowski Michel Hehn Cédric Baumier Franck Fortuna Damjan Krizmancic Luigi Stebel Rudi Sergo Giuseppe Cautero 《Journal of synchrotron radiation》2017,24(4):886-897
The SOLEIL synchrotron radiation source is regularly operated in special filling modes dedicated to pump–probe experiments. Among others, the low‐α mode operation is characterized by shorter pulse duration and represents the natural bridge between 50 ps synchrotron pulses and femtosecond experiments. Here, the capabilities in low‐α mode of the experimental set‐ups developed at the TEMPO beamline to perform pump–probe experiments with soft X‐rays based on photoelectron or photon detection are presented. A 282 kHz repetition‐rate femtosecond laser is synchronized with the synchrotron radiation time structure to induce fast electronic and/or magnetic excitations. Detection is performed using a two‐dimensional space resolution plus time resolution detector based on microchannel plates equipped with a delay line. Results of time‐resolved photoelectron spectroscopy, circular dichroism and magnetic scattering experiments are reported, and their respective advantages and limitations in the framework of high‐time‐resolution pump–probe experiments compared and discussed. 相似文献
76.
Fabien Joux Wade H. Jeffrey Maher Abboudi Jacques Neveux Mireille Pujo-Pay Louise Oriol Jean-Jacques Naudin 《Photochemistry and photobiology》2009,85(3):783-793
The high content in nutrients of freshwater outflows induces highly productive and buoyant plumes spreading over marine waters (MW). As a consequence, the growth of organisms developing in these low‐salinity waters (LSW) might be potentially affected by UV‐R (280–400 nm). This study investigated the penetration of UV‐R and its impact on net community production (NCP) and bacterial protein (BPROTS) and DNA (BDNAS) synthesis in mesotrophic‐LSW formed from the Rhône River and in oligotrophic MW of the Northwestern Mediterranean Sea (Gulf of Lions) in May 2006. High concentrations of chlorophyll a (up to 8 μg L?1) measured in the LSW (<37.8 psu, 0–10 m) were the main factor influencing the diffuse attenuation coefficients (Kd) of both UV‐R and photosynthetically active radiation (PAR). The mean ratio of the Kd measured between the LSW and the MW increased with wavelength from 2.4 at 305 nm to 2.9 at 380 nm and 3.1 for PAR indicating more similarity in the UV region. NCP was severely inhibited by UV‐R at the surface of the LSW, whereas no effect was measured in the surrounding MW. In contrast, BPROTS and BDNAS were affected deeper by UV‐R in the MW (up to 8 m depth) compared to the LSW where inhibition was only observed at the surface. Differences in response of bacteria in LSW and MW are largely explained by differences in UV‐R transparency; however, transplant experiments indicate that bacterial assemblages from the MW were also more sensitive to UV‐R than those present in the LSW. We also observed that higher activity of bacteria after nutrient additions increased their sensitivity to UV‐R during the day, but favored their recovery during the night incubation period for both LSW and MW. Results suggest that riverine and nutrient inputs may alter the effects of UV‐R on microbial activity by attenuating the UV‐R penetration and by modifying the physiology of bacteria. 相似文献
77.
Jordan N Lomenech C Marmier N Giffaut E Ehrhardt JJ 《Journal of colloid and interface science》2009,329(1):17-23
Sorption of selenium(IV) and silicic acid onto magnetite (Fe(3)O(4)) was investigated in binary systems, with concentrations of silicic acid under the solubility limit of amorphous silica. Using the double diffuse layer model (DDLM), surface complexation constants of selenium(IV) and H(4)SiO(4) onto magnetite were extracted using Fiteql 4.0. Then, prediction curves of the sorption of selenium(IV) in the presence of silicic acid onto magnetite were obtained, using the calculated surface complexation constants. Finally, laboratory experiments were performed and showed a competition between selenium(IV) and silicic acid for the surface sites of magnetite. Experimental results matched the model predictions, confirming its ability to model qualitatively and quantitatively the ternary system. 相似文献
78.
Moussa Mbaye Mame Diabou Gaye Seye Atanasse Coly Alphonse Tine Jean-Jacques Aaron 《Analytical and bioanalytical chemistry》2009,394(4):1089-1098
The photochemically induced fluorescence (PIF) spectral properties of α-cypermethrin in organic solvents (hexane, dichloromethane,
acetonitrile, ethanol) and in cyclodextrin aqueous solutions (β-CD and 2-hydroxypropyl-β-CD, 2-HP-β-CD) were investigated.
The photolysis kinetics of α-cypermethrin were evaluated in the various media. The PIF signal was found to be significantly
enhanced in the CD media relative to the organic solvents. The stoichiometry and the formation constants of the α-cypermethrin
inclusion complexes formed with the CDs were determined. The analytical performances of the PIF method were improved in the
presence of HP-β-CD relative to the other media, and a CD-enhanced PIF analytical method was developed. The limits of detection
and limits of quantification ranged, respectively, between 6 and 98 ng/mL and between 24 and 343 ng/mL, depending on the medium.
Application to the analysis of tap water and Senegal natural water samples collected close to agricultural areas and spiked
with α-cypermethrin yielded satisfactory recoveries going from about 77% to 98%. An interference study of foreign species,
including pesticides and inorganic ions likely to be present in natural waters, was also carried out.
Figure Photolysis reaction of α-cypermethrin in presence of HP-β-CD 相似文献
79.
Thi Thu Van Nguyen Jean-Jacques Strodiot Van Hien Nguyen 《Journal of Global Optimization》2009,44(2):175-192
In this article we present a new and efficient method for solving equilibrium problems on polyhedra. The method is based on
an interior-quadratic proximal term which replaces the usual quadratic proximal term. This leads to an interior proximal type
algorithm. Each iteration consists in a prediction step followed by a correction step as in the extragradient method. In a
first algorithm each of these steps is obtained by solving an unconstrained minimization problem, while in a second algorithm
the correction step is replaced by an Armijo-backtracking linesearch followed by an hyperplane projection step. We prove that
our algorithms are convergent under mild assumptions: pseudomonotonicity for the two algorithms and a Lipschitz property for
the first one. Finally we present some numerical experiments to illustrate the behavior of the proposed algorithms. 相似文献
80.
Tailoring the porous hierarchy of titanium phosphates 总被引:1,自引:0,他引:1
Ren TZ Yuan ZY Azioune A Pireaux JJ Su BL 《Langmuir : the ACS journal of surfaces and colloids》2006,22(8):3886-3894
First hierarchical titanium phosphate (TiPO) materials with multiple porosities of different lengths (meso-macroporous and meso-macro-macroporous) were synthesized by the self-formation process. The further tuning of the porous hierarchy by using the poly(ethylene oxide) surfactant technique was demonstrated. The macroporous structure (50-160 nm in size) of TiPO with mesoporous walls could be self-formed in the absence of any templatable agents, including surfactant molecules. On the basis of spontaneous structurization, the addition of a small quantity of nonionic poly(ethylene oxide) surfactant (e.g., 5%) led to an improvement in macroporosity in abundance and in regularity with a slight enlargement in macropore sizes to 80-250 nm. Interestingly, a secondary, larger macropore system with parallel channels 500-1000 nm in size was generated when the synthesis was performed with moderately increasing the content of surfactant (10%), giving rise to an unprecedented trimodal meso-macro-macroporous structure. A uniform three-dimensional co-continuous macroporous structure with accessible wormhole-like mesoporous walls was synthesized by using the higher content of surfactants. This is a direct demonstration of tailoring the porous hierarchy of different lengths integrated in one solid body by fine-tuning the self-formation process and the participation of surfactant. The synthesized hierarchical titanium phosphates possess interesting optical and acidic properties, which should be significant for large application potential from catalysis and separation to electrochromic devices, fuel cells, and bioactive materials. 相似文献