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991.
Divalent complexes of iron and cobalt with new, monoanionic tripodal amido-polyphosphine ligands have been thoroughly characterized, and XRD analysis reveals geometries that are distinct for this class of ligand. 相似文献
992.
2,4-Difluorotoluene is unusual among hydrofluorocarbons because it is shaped like the DNA base thymine. It was first synthesised as a nucleotide analogue and incorporated into DNA a decade ago. Although it is a nonpolar molecule, it was found to be replicated by DNA polymerase enzymes as if it were thymine. We concluded that replication of DNA base pairs can occur without Watson-Crick hydrogen bonds, and hypothesised that steric effects, rather than these hydrogen bonds, were the main arbiters of DNA replication fidelity. A debate was initiated then, with claims by some that the molecule is polar and forms hydrogen bonds with adenine, thus supporting the hydrogen bonding theory of DNA replication. Here we discuss the evolution of this debate, and reflect on the relevant data that have since come from hundreds of papers and dozens of laboratories. Although discussion on this topic continues, the steric hypothesis for DNA replication is now widely accepted among biochemists, and the changing paradigm has been reflected in textbooks. 相似文献
993.
Lyskawa J Sallé M Balandier JY Le Derf F Levillain E Allain M Viel P Palacin S 《Chemical communications (Cambridge, England)》2006,(21):2233-2235
The formation of the two dimeric species [(TTF)2]+* and (TTF+*)2 can be monitored by complexation of Na+ on a calix[4]arene-TTF assembly. 相似文献
994.
The ultrafast ground state recovery (GSR) dynamics of the radical cation of perylene, Pe(*+), generated upon bimolecular photoinduced electron transfer in acetonitrile, has been investigated using pump-pump-probe spectroscopy. With 1,4-dicyanobenzene as electron acceptor, the free ion yield is substantial and the GSR dynamics of Pe(*+) was found to depend on the time delay between the first and second pump pulses, Deltat(12), i.e., on the "age" of the ion. At short Deltat(12), the GSR dynamics is biphasic, and at Deltat(12) larger than about 500 ps, it becomes exponential with a time constant around 3 ps. With trans-1,2-dicyanoethylene as acceptor, the free ion yield is essentially zero and the GSR dynamics of Pe(*+) remains biphasic independently of Deltat(12). The change of dynamics observed with 1,4-dicyanobenzene is ascribed to the transition from paired to free solvated ion, because in the pair, the excited ion has an additional decay channel to the ground state, i.e., charge recombination followed by charge separation. The rate constants deduced from the analysis of these GSR dynamics are all fully consistent with this hypothesis. 相似文献
995.
Preat J Jacquemin D Wathelet V André JM Perpète EA 《The journal of physical chemistry. A》2006,110(26):8144-8150
The UV absorption spectra of more than 80 substituted coumarins and chromones have been investigated with the PCM-TD-DFT theoretical scheme using three hybrid functionals (O3LYP, B3LYP, and PBE0) and taking into account methanol or ethanol solvation effects. For most of the studied derivatives, there are at least two allowed excited states presenting a strong oscillator strength in the UV region. The first allowed excitation is associated to a HOMO-LUMO transition whereas the second corresponds to a transition from the HOMO-1 to the LUMO. Both involve a charge transfer from the benzenic cycle to the pyranone moiety. Statistically treating the PBE0 results allows a prediction of the lambda(max) with small standard deviations: in methanol, 6 nm (0.07 eV) for the first excitation (lambda(max)(1)) and 5 nm (0.08 eV) for the second one (lambda(max)(2)), whereas in ethanol 6 nm (0.08 eV) for (lambda(max)(1)) and 6 nm (0.13 eV) for (lambda(max)(2)). 相似文献
996.
Ge N Fogel P Young SS Austin RE Wegrzyniak E Connelly JA 《Combinatorial chemistry & high throughput screening》2006,9(6):465-472
The goal of combinatorial chemistry is to simultaneously synthesize sets of compounds possessing properties that are then distinguished through screening. As the size of a compound set increases, data analysis becomes more challenging. Analysis of Variance (ANOVA) is an accepted statistical method that offers a straightforward solution to this problem. Two steps encountered by combinatorial scientists appear well suited to ANOVA: the prediction of synthetic outcomes (purity and yield) of set members and the analysis of screening data to identify combinations of reagent inputs that result in molecules with a desired property. To illustrate, a subset of a combinatorial array, referred to as a reaction rehearsal set, is evaluated to create a model predictive of the individual synthetic outcomes of the full matrix. In a second exercise, the biochemical screening data obtained from a combinatorial library is analyzed to identify reagent interactions that result in molecules possessing the sought activity. 相似文献
997.
998.
999.
Peter Kop?anský Martina Koneracká Vlasta Závišová Katalin Fodor-Csorba Anikó Vajda Eric Beaugnon 《Journal of magnetism and magnetic materials》2010,322(22):3696-3700
The studied ferronematic is a nematic liquid crystal (ZLI1695) of low negative anisotropy of the diamagnetic susceptibility (χa<0) doped with the magnetic particles Fe3O4. Structural instabilities are interpreted within Burylov and Raikher's theory. The high magnetic fields were oriented perpendicular (Freedericksz transition) or parallel to the initial director. Using capacitance measurements the Freedericksz threshold magnetic field of the ferronematic BFN, and the critical magnetic field Bmax, at which the initial parallel orientation between the director and the magnetic moment of magnetic particles breaks down, have been determined. The values of these quantities have been used to estimate the surface density of the anchoring energy W of liquid crystal molecules on the surface of the magnetic particles. The obtained values indicate a soft anchoring of the liquid crystal on the magnetic particles with a preferred parallel orientation of the magnetic moment of magnetic particles and the director. 相似文献
1000.
We show that the nonequilibrium entropy production for a driven quantum system is larger than the Bures length, the geometric distance between its actual state and the corresponding equilibrium state. This universal lower bound generalizes the Clausius inequality to arbitrary nonequilibrium processes beyond linear response. We further derive a fundamental upper bound for the quantum entropy production rate and discuss its connection to the Bremermann-Bekenstein bound. 相似文献