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711.
Dr. Joaquín Calbo Juan Aragó Dr. Francisco Otón Dr. Vega Lloveras Dr. Marta Mas‐Torrent Dr. José Vidal‐Gancedo Prof. Jaume Veciana Prof. Concepció Rovira Prof. Enrique Ortí 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16656-16664
This work presents a joint theoretical and experimental characterisation of the structural and electronic properties of two tetrathiafulvalene (TTF)‐based acceptor–donor–acceptor triads (BQ–TTF–BQ and BTCNQ–TTF—BTCNQ; BQ is naphthoquinone and BTCNQ is benzotetracyano‐p‐quinodimethane) in their neutral and reduced states. The study is performed with the use of electrochemical, electron paramagnetic resonance (EPR), and UV/Vis/NIR spectroelectrochemical techniques guided by quantum‐chemical calculations. Emphasis is placed on the mixed‐valence properties of both triads in their radical anion states. The electrochemical and EPR results reveal that both BQ–TTF–BQ and BTCNQ–TTF–BTCNQ triads in their radical anion states behave as class‐II mixed‐valence compounds with significant electronic communication between the acceptor moieties. Density functional theory calculations (BLYP35/cc‐pVTZ), taking into account the solvent effects, predict charge‐localised species (BQ . ?–TTF–BQ and BTCNQ . ?–TTF–BTCNQ) as the most stable structures for the radical anion states of both triads. A stronger localisation is found both experimentally and theoretically for the BTCNQ–TTF–BTCNQ anion, in accordance with the more electron‐withdrawing character of the BTCNQ acceptor. CASSCF/CASPT2 calculations suggest that the low‐energy, broad absorption bands observed experimentally for the BQ–TTF–BQ and BTCNQ–TTF–BTCNQ radical anions are associated with the intervalence charge transfer (IV‐CT) electronic transition and two nearby donor‐to‐acceptor CT excitations. The study highlights the molecular efficiency of the electron‐donor TTF unit as a molecular wire connecting two acceptor redox centres. 相似文献
712.
Dr. Ivan E. Kareev Dr. Elena Laukhina Dr. Vyacheslav P. Bubnov Dr. Vyacheslav M. Martynenko Vega Lloveras Dr. José Vidal‐Gancedo Dr. Marta Mas‐Torrent Prof. Jaume Veciana Prof. Concepció Rovira 《Chemphyschem》2013,14(8):1670-1675
We show that electron transfer from the perchlorotriphenylmethide anion (PTM?) to Y@C82(C2v) is an instantaneous process, suggesting potential applications for using PTM? to perform redox titrations of numerous endohedral metallofullerenes. The first representative of a Y@C82‐based salt containing the complex cation was prepared by treating Y@C82(C2v) with the [K+([18]crown‐6)]PTM? salt. The synthesis developed involves the use of the [K+([18]crown‐6)]PTM? salt as a provider of both a complex cation and an electron‐donating anion that is able to reduce Y@C82(C2v). For the first time, the molar absorption coefficients for neutral and anionic forms of the pure isomer of Y@C82(C2v) were determined in organic solvents with significantly different polarities. 相似文献
713.
Previous work has reported on the identification and characterization of the hexapeptide ligands HWRGWV, HYFKFD, and HFRRHL for the affinity capture of IgG through specific binding to its Fc fragment. This paper addresses issues related to the successful application of these ligands, on a commercial methacrylate chromatographic resin, for the purification of IgG from mammalian cell culture fluids. The concentrations of sodium chloride and sodium caprylate in the binding buffer were optimized to maximize the purity and yield of IgG upon elution. Screening of several regeneration conditions found that either 2M guanidine-HCl or a combination of 0.85% phosphoric acid followed by 2M urea resulted in complete recovery of the IgG adsorption capacity and that the column could be reused over many cycles. The hexapeptide ligands were used for the purification of humanized and chimeric monoclonal antibodies from two commercial CHO cell culture fluids. The chimeric MAb of IgG1 subclass was purified using the HWRGWV resin whereas the humanized MAb of IgG4 subclass was purified using the HWRGWV, HYFKFD and HFRRHL resins. The purities and yields obtained for both the MAbs were found to be higher than 94% and 85% respectively. These results compare well with the yields and purities obtained using Protein G columns. The residual DNA and host cell protein reduction obtained by the HWRGWV resin was in the range of 4 log reduction value (LRV) and 2 LRV respectively, comparable to those reported for Protein A resins. The dynamic binding capacity of all three peptide resins for the humanized monoclonal antibody was in the range of 20mg/mL. 相似文献
714.
Increasing the isomerisation kinetics of azo dyes by chemical bonding to liquid-crystalline polymers
Garcia-Amorós J Finkelmann H Velasco D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(23):6518-6523
It is well known that the proper substitution of the azobenzene core allows tuning the thermal cis-to-trans isomerisation kinetics of azo dyes. The thermal isomerisation process of nitro-substituted azobenzenes is accelerated up to 13 times with respect to that in the common isotropic solvents when they are doped in nematic low molar mass liquid crystals. This kinetic acceleration is even stronger when these azo dyes are covalently linked to a nematic siloxane polymer. In this environment, the isomerisation process is accelerated more than 10(3) times. This effect is presented herein for the first time. The possible application of the networks obtained as possible photo-actuators has been also considered. 相似文献
715.
F. de Soto J. C. Anglès d’Auriac J. Carbonell 《The European Physical Journal A - Hadrons and Nuclei》2011,47(4):57
We present the results of the quantum field theory approach to the nuclear Yukawa model obtained by standard lattice techniques.
We have considered the simplest case of two identical fermions interacting via a scalar meson exchange. Calculations have
been performed using Wilson fermions in the quenched approximation. We found the existence of a critical coupling constant
above which the model cannot be numerically solved. The range of the accessible coupling constants is below the threshold
value for producing two-body bound states. Two-body scattering lengths have been obtained and compared to the non-relativistic
results. 相似文献
716.
717.
718.
719.
Nonlinear Dynamics - For a $$C^{m+1}$$ differential system on $$\mathbb {R}^n$$ , we study the limit cycles that can bifurcate from a zero–Hopf singularity, i.e., from a singularity with... 相似文献
720.
We analyse the existence of symmetric periodic orbits of the two-electron atom. The results obtained show that there exist six families of periodic orbits that can be prolonged from a continuum of periodic symmetric orbits. The main technique applied in this study is the continuation method of Poincaré. 相似文献