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81.
The authors analyze the long-time self-diffusion of charge-stabilized colloidal macroions in nondilute suspensions using a mode-coupling scheme developed for multicomponent suspensions of interacting Brownian spheres. In this scheme, all ionic species, including counterions and electrolyte ions, are treated on an equal footing as charged hard spheres undergoing overdamped Brownian motion. Hydrodynamic interactions between all ions are accounted for on the far-field level. We show that the influence on the colloidal long-time self-diffusion coefficient arising from the relaxation of the microionic atmosphere surrounding the colloids, the so-called electrolyte friction effect, is usually insignificant in comparison with the friction contributions arising from direct and hydrodynamic interactions between the colloidal particles. This finding is true even for small colloid concentrations unless the mobility difference between colloidal particles and microions is not large. Furthermore, we observe an interesting nonmonotonic density dependence of the colloidal long-time self-diffusion coefficient in suspensions with low amount of added salt. We show that this unusual density dependence is due to colloid-colloid hydrodynamic interactions. 相似文献
82.
Dr. Damien Lhenry Dr. Manuel Larrouy Dr. Claire Bernhard Dr. Victor Goncalves Dr. Olivier Raguin Dr. Peggy Provent Dr. Mathieu Moreau Dr. Bertrand Collin Dr. Alexandra Oudot Dr. Jean‐Marc Vrigneaud Dr. François Brunotte Dr. Christine Goze Prof. Franck Denat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):13091-13099
In molecular imaging, multimodal imaging agents can provide complementary information, for improving the accuracy of disease diagnosis or enhancing patient management. In particular, optical/nuclear imaging may find important preclinical and clinical applications. To simplify the preparation of dual‐labeled imaging agents, we prepared versatile monomolecular multimodal imaging probe (MOMIP) platforms containing both a fluorescent dye (BODIPY) and a metal chelator (polyazamacrocycle). One of the MOMIP was conjugated to a cyclopeptide (i.e., octreotide) and radiolabeled with 111In. In vitro and in vivo studies of the resulting bioconjugate were conducted, highlighting the potential of these BODIPY‐based bimodal probes. This work also confirmed that the biovector and/or the bimodal probes must be chosen carefully, due to the impact of the MOMIP on the overall properties of the resulting imaging agent. 相似文献
83.
84.
Infrared spectra simulations require ab initio techniques to get reliable intensities. On the other hand, recent force fields can provide accurate molecular geometries and frequencies. Therefore, it is suggested that these new force fields could be used to simulate infrared spectra, dipole-moment surfaces being described at high levels of theory in order to get satisfactory intensities. As pointed out, for a system with N atoms, the cost of such a simulation would be reduced N-fold with respect to standard quantum approaches. Preliminary calculations based on this scheme are reported here. Encouraging results are obtained since no significant lost of accuracy is noted on going from the ab initio to the molecular mechanics potential energy surface. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 705–711, 1998 相似文献
85.
A Redox‐Active Bridging Ligand to Promote Spin Delocalization,High‐Spin Complexes,and Magnetic Multi‐Switchability 下载免费PDF全文
Xiaozhou Ma Dr. Elizaveta A. Suturina Dr. Siddhartha De Dr. Philippe Négrier Mathieu Rouzières Dr. Rodolphe Clérac Dr. Pierre Dechambenoit 《Angewandte Chemie (International ed. in English)》2018,57(26):7841-7845
A dinuclear CoII complex, [Co2(tphz)(tpy)2]n+ (n=4, 3 or 2; tphz: tetrapyridophenazine; tpy: terpyridine), has been assembled using the redox‐active and strongly complexing tphz bridging ligand. The magnetic properties of this complex can be tuned from spin‐crossover with T1/2≈470 K for the pristine compound (n=4) to single‐molecule magnet with an ST=5/2 spin ground state when once reduced (n=3) to finally a diamagnetic species when twice reduced (n=2). The two successive and reversible reductions are concomitant with an increase of the spin delocalization within the complex, promoting remarkably large magnetic exchange couplings and high‐spin species even at room temperature. 相似文献
86.
We study reduction of generalized complex structures. More precisely, we investigate the following question. Let J be a generalized complex structure on a manifold M, which admits an action of a Lie group G preserving J. Assume that M0 is a G-invariant smooth submanifold and the G-action on M0 is proper and free so that MG?M0/G is a smooth manifold. Under what condition does J descend to a generalized complex structure on MG? We describe a sufficient condition for the reduction to hold, which includes the Marsden–Weinstein reduction of symplectic manifolds and the reduction of the complex structures in Kähler manifolds as special cases. As an application, we study reduction of generalized Kähler manifolds. 相似文献
87.
Cartigny B Azaroual N Imbenotte M Mathieu D Parmentier E Vermeersch G Lhermitte M 《Talanta》2008,74(4):1075-1078
The determination and quantification of glyphosate in serum using (1)H NMR spectroscopy is reported. This method permitted serum samples to be analysed without derivatization or any other sample pre-treatment, using 3-trimethylsilyl 2,2',3,3'-tetradeuteropropionic acid (TSP-d(4)) as a qualitative and quantitative standard. Characterization of the herbicide N-(phosphonomethyl)glycine was performed by analysing chemical shifts and coupling constant patterns. Quantification was performed by relative integration of CH(2)-P protons to the TSP-d(4) resonance peak. The method was tested for repeatability (n=5) and yielded coefficients of variation of 1% and 3%, respectively: detection and quantification limits were also determined and were 0.03 and 0.1mmol/L, respectively. The method was applied to the quantification of glyphosate in a case of acute poisoning. 相似文献
88.
Highly concentrated colloidal suspensions exhibit a discontinuous shear-thickening behaviour. The transition from a low to a high viscosity state is associated to a large energy dissipation. This effect could find applications in structural damping while the viscosity increase brings added stiffness. In the present work, highly concentrated suspensions of monodisperse spherical silica particles in polyethylene glycol were selected for their strong thickening at low critical shear rates. Their damping properties were characterized by measuring the energy dissipated per cycle at low frequency (below 2 Hz) during oscillatory tests using a rheometer. The influence of parameters such as particle concentration, size and frequency was investigated. Damping was found to overcome that of benchmark elastomeric materials only in high frequencies and high strain domains. 相似文献
89.
Amandine Cournet Marie-Line Délia Alain Bergel Christine Roques Mathieu Bergé 《Electrochemistry communications》2010,12(4):505-508
Most bacteria known to be electrochemically active have been harvested in the anodic compartments of microbial fuel cells (MFCs) and are able to use electrodes as electron acceptors. The reverse phenomenon, i.e. using solid electrodes as electron donors, is not so widely studied. To our knowledge, most of the electrochemically active bacteria are Gram-negative. The present study implements a transitory electrochemical technique (cyclic voltammetry) to study the microbial catalysis of the electrochemical reduction of oxygen. It is demonstrated that a wide range of aerobic and facultative anaerobic bacteria are able to catalyze oxygen reduction. Among these electroactive bacteria, several were Gram-positive. The transfer of electrons was direct since no activity was obtained with the filtrate. These findings, showing a widespread property among bacteria including Gram-positive ones, open new and interesting routes in the field of electroactive bacteria research. 相似文献
90.
Philippe Gros Sabine Choppin Julien Mathieu Yves Fort 《The Journal of organic chemistry》2002,67(1):234-237
The determination of the initial deprotonation site of 2-chloro- and 2-methoxypyridine during reaction with BuLi-LiDMAE has been investigated. A series of experiments on deuterated regioisomers revealed a direct lithiation at C-6 excluding a potential first classical ortholithiation and lithium equilibration in the reaction medium. These results suggested that the formation of lithium aggregates at the neighboring of the pyridinic nitrogen atom favored BuLi delivery at C-6 as well as 6-lithio intermediate stabilization. 相似文献