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91.
Isoprene–Styrene Chain Shuttling Copolymerization Mediated by a Lanthanide Half‐Sandwich Complex and a Lanthanidocene: Straightforward Access to a New Type of Thermoplastic Elastomers 下载免费PDF全文
Dr. Andreia Valente Dr. Gregory Stoclet Dr. Fanny Bonnet Prof. André Mortreux Prof. Marc Visseaux Prof. Philippe Zinck 《Angewandte Chemie (International ed. in English)》2014,53(18):4638-4641
A lanthanide half‐sandwich complex and a ansa lanthanidocene have been assessed for isoprene–styrene chain shuttling copolymerization with n‐butylethylmagnesium (BEM). In the presence of 1 equiv BEM, a fully amorphous multiblock microstructure of soft and hard segments is achieved. The microstructure consists of poly(isoprene‐co‐styrene) blocks, with hard blocks rich in styrene and soft blocks rich in isoprene. The composition of the blocks and the resulting glass transition temperatures (Tg) can be easily modified by changing the feed and/or the relative amount of the catalysts, highlighting a new class of thermoplastic elastomers (TPEs) with tunable transition temperatures. The materials self‐organize into nanostructures in the solid state. 相似文献
92.
We have synthesised novel oligo(ethylene glycol), CF3-terminated switching self-assembled monolayers, which allow the force experienced by a hydrophobic object to be controlled via the ionic strength of the environment. 相似文献
93.
Marc Bonnet 《International Journal of Solids and Structures》2009,46(11-12):2275-2292
This article concerns an extension of the topological derivative concept for 2-D potential problems involving penetrable inclusions, whereby a cost function J is expanded in powers of the characteristic size ε of a small inclusion. The O(ε4) approximation of J is established for a small inclusion of given location, shape and conductivity embedded in a 2-D region of arbitrary shape and conductivity, and then generalized to several such inclusions. Simpler and more explicit versions of this result are obtained for a centrally-symmetric inclusion and a circular inclusion. Numerical tests are performed on a sample configuration, for (i) the O(ε4) expansion of potential energy, and (ii) the identification of a hidden inclusion. For the latter problem, a simple approximate global search procedure based on minimizing the O(ε4) approximation of J over a dense search grid is proposed and demonstrated. 相似文献
94.
Bonnet LG Douthwaite RE Hodgson R Houghton J Kariuki BM Simonovic S 《Dalton transactions (Cambridge, England : 2003)》2004,(21):3528-3535
The synthesis and structures of chiral N-heterocyclic carbene (NHC)-N-donor complexes of silver(I) and palladium(II) are reported. The X-ray structure of an NHC-imine silver(I) complex [((nPr)CN(CHPh))AgBr](2) exhibits an Ag(2)Br(2) dimer motif where the imine group is not coordinated to the silver atom. Reaction between 2 and [PdCl(2)(MeCN)(2)] gives the palladium(II) complex [(kappa(2)-(nPr)CN(CHPh))PdCl(2)](3) that contains a chelating NHC-imine ligand as shown by single-crystal X-ray diffraction. Slow hydrolysis of related complexes [(kappa(2)-(nPr)CN(CHPh))PdCl(2)](3) and [(kappa(2)-((Ph)(2)CH)CN(CHPh))PdCl(2)](4) using triethylammonium chloride and water lead to the precipitation of single crystals of insoluble NHC-amino palladium(II) complexes [(kappa(2)-(nPr)CN(H(2)))PdCl(2)](6) and [(kappa(2)-((Ph)(2)CH)CN(H(2)))PdCl(2)](7), respectively. In the solid state, complexes 6 and 7 both exhibit intermolecular hydrogen bonding between chlorine and an amino-hydrogen atom resulting in an infinite chain structure. Substitution of an amino hydrogen for an ethyl group gives the soluble complex [(kappa(2)-(iPr)CN((H)Et))PdCl(2)](12). Reaction between two equivalents of 2 and [PdCl(2)(MeCN)(2)] gives the di-NHC complex [(kappa(1)-(nPr)CN(CHPh))(2)PdCl(2)](5) that does not contain a coordinated imine as shown by single crystal X-ray diffraction. Conproportionation between 5 and an equivalent of [PdCl(2)(MeCN)(2)] to does not occur at temperatures up to 100 degrees C in CD(3)CN. 相似文献
95.
In this paper, we analyze the microstructural effects on non linear elastic and periodic composites within the framework of asymptotic homogenization. We assume that the constitutive laws of the individual constituents derive from strain potentials. The microstructural effects are incorporated by considering the higher order terms, which come from the asymptotic series expansion. The complete solution at any order requires the resolution of a chain of cell problems in which the source terms depend on the solution at the lower order. The influence of these terms on the macroscopic response of the non linear composite is evaluated in the particular case of a stratified microstructure. The analytic solutions of the cell problems at the first and second order are provided for arbitrary local strain–stress laws which derive from potentials. As classically, the non-linear dependence on the applied macroscopic strain is retrieved for the solution at the first order. It is proved that the second order term in the expansion series also exhibits a non linear dependence with the macroscopic strain but linearly depends on the gradient of macroscopic strain. As a consequence, the macroscopic potential obtained by homogenization is a quadratic function of the macroscopic strain gradient when the expansion series is truncated at the second order. This model generalizes the well known first strain gradient elasticity theory to the case of non linear elastic material. The influence of the non local correctors on the macroscopic potential is investigated in the case of power law elasticity under macroscopic plane strain or antiplane conditions. 相似文献
96.
Gd3+ complexes are widely used as contrast enhancing agents in medical magnetic resonance imaging (MRI). In recent years, new fields have emerged in their development. The general tendency of using higher magnetic fields in biomedical and clinical MRI for a better signal to noise ratio calls for new contrast agents specifically optimized for such high field applications. Molecular imaging, aiming at the non-invasive visualisation of expression and function of bioactive molecules, requires imaging probes that provide a specific magnetic response to a particular molecular event. Finally, bimodal imaging may allow for combining the excellent resolution of MRI with a good sensitivity of other imaging modalities, such as optical methods. It requires bimodal imaging probes that satisfy requirements for both modalities within a single molecule. Here we review our latest efforts to develop novel lanthanide-based contrast agents in these specific fields and demonstrate the possibilities offered by lanthanide coordination chemistry. 相似文献
97.
The relative spatial distribution and motion with respect to Gd3+ of the 1H and 19F nuclei in the acetate ion and its fluorine derivatives are studied in D2O solutions through the paramagnetic relaxation rate enhancements (PREs) of these nuclei. We derive general theoretical expressions of the longitudinal PRE in terms of the analytical concentrations of metal and ligands, formation constants of the complexes, metal–nucleus distances, and coordination lifetimes of the ligands. The observed formation constants of the 1 metal: 1 ligand complexes markedly decrease with increasing number of fluorine atoms, the electronegativity of which reduces the negative partial charge of the coordinating COO? group. The coordination lifetimes are very short at the scale of the relaxation times of the protons of metal bound acetate, that is, shorter than about 10 μs. The average distance of the acetate protons from Gd3+ is in fair agreement with independent crystallographic determination. The release of free Gd3+ from the very stable Gddtpa (dtpa=diethylene‐triaminepentaacetate) complex caused by the competition of Zn2+ for dtpa, is evidenced by an increase of the PREs with Zn2+ concentration. The observed PRE increase is consistent with the known equilibrium constants governing the speciation involving Gd3+, Zn2+, and dtpa. The present case study illustrates a method which easily yields experimental tunable properties suitable to test the ongoing theories of lanthanide Ln3+ complexation in solution. 相似文献
98.
Destandau E Vial J Jardy A Hennion MC Bonnet D Lancelin P 《Analytica chimica acta》2006,572(1):102-112
The robustness study of the reversed-phase liquid chromatographic method developed for the quantitative analysis of carboxylic acids is a real asset to prepare method transfer because it provides an indication of its reliability during routine use. Indeed, it was possible to predict the consequences of small variations in operating conditions on the responses. The design of experiments approach was applied to model the effects and interactions of a high number of factors varying simultaneously with a limited number of runs. First we identified the factors which potentially affect the chromatographic responses used for carboxylic acids quantitation: detection wavelength (λ), column temperature (T), acetonitrile ratio in mobile phase (Me), duration of the plateau before the gradient (L) and gradient slope (S). Then we estimated the order of magnitude of realistic variations to assign factor levels. Finally a central composite design was carried out around the nominal conditions defined during method optimization. The statistical treatment of responses (retention factors, and concentrations) showed that the column temperature, the acetonitrile ratio in the mobile phase, the duration of the plateau before the gradient and the gradient slope were the most influent factors. The building of the robust domain from response-surfaces allowed us to give tolerance limits for the factors (216 nm < λ < 222 nm, 49.3 °C < T < 51.4 °C, 4.90% < Me < 5.18%, v/v, 4.5 min < L < 5.4 min, 9% < S < 11%) for which the performances of the method were maintained. 相似文献
99.
100.
Bonnet L Larrégaray P Rayez JC Gonzalez-Lezana T 《Physical chemistry chemical physics : PCCP》2006,8(34):3951-3954
For complex-forming chemical reactions, such as atom-diatom insertion reactions, quantum scattering and quantum statistical calculations usually predict sharp forward/backward peaks in the Differential Cross Sections (DCS). Conversely, the corresponding classical calculations are unable to reproduce these peaks. We show here that the basic reason for such an intriguing failure is that parity conservation is ignored in classical mechanics. A by-product of the analysis is a simple parity-restoring approximation that might significantly increase the ability of classical mechanics to describe DCSs over the whole angular range for the title processes. 相似文献