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871.
The adsorption/desorption process of borate was studied at Pt(111) in acidic solution by cyclic voltammetry. A so-called butterfly
wave in the cyclic voltammogram of Pt(111) in HClO4 shifted to negative direction upon the addition of boric acid with the disappearance of its sharp spikes. The shift in potential
was found to be −57 mV with a tenfold increase of boric acid concentration. This illustrates that this anomalous wave is due
to borate adsorption/desorption by a one-electron transfer process. The borate adsorption/desorption wave was observed to
shift by −63 mV/pH. At pH>3, the anomalous wave splits forming two separate waves, depending on the pH and the scan rate.
The appearance of two waves is assigned to the change in the adsorption mode of borate or the participation of OH in the adsorption
process. 相似文献
872.
Vijayasarathi Nagarajan Barbara Müller Oksana Storcheva Klaus Köhler Andreas Pöppl 《Research on Chemical Intermediates》2007,33(8):705-724
Interactions and binding sites of the solvent molecules chloroform and ethanol to bis(acetylacetonate)oxovanadium(IV) (VO(acac)2) complexes in (frozen) solutions have been investigated by pulsed electron nuclear double resonance, sum peak electron spin
echo envelope modulation and hyperfine sublevel correlation spectroscopy. The experimental proton hyperfine coupling data
of coordinating solvent molecules have been interpreted using quantum chemical calculations (density functional theory). Experimental
and computed hyperfine couplings indicate that ethanol coordinates to vanadium in the equatorial plane of VO(acac)2 and chloroform interacts via hydrogen bonding to oxygens of the acac ligands. 相似文献
873.
Summary The coupling of carbon dioxide supercritical fluid chromatography with Fourier transform infrared spectrometry (SFC-FTIR)
is a powerful tool for the separation and on-line identification of non-volatile compounds. The IR transparency of carbon
dioxide in the Fermi resonance bands region versus its density has been studied. Functional groups with stretching vibrations
outside the transparent window of carbon dioxide are examined. SFC-FTIR separations allow Gram-Schmidt reconstruction chromatograms
or IR window chemigrams with high quality spectra to be obtained. This SFC-FTIR lightpipe (flow cell, beam condensing optics,
narrow band detector) has allowed detection limits of 250ng for benzonitrile and 70ng for methyl benzoate to be reached. The
feasibility of very rapid SFC-FTIR separations is shown along with the subsequent peak spectra. 相似文献
874.
The effects of crown ethers (6 and 7) on the reactions of sodium (2a) and potassium enolates (2b) of 2-ethoxycarbonylcyclohexanone (1) with isopropyl iodide in dimethylsulfoxide and dimethoxyethane have been investigated. When the addition of crown ether promoted dissociation of ion pair 2 in either of the two solvents, the total rate of reaction (kt) increased and the ratio of carbon- (3) to oxygen-alkylation (4 and 5) products decreased. The results are consistent with the involvement of both the ion pair and more dissociated species in alkylation and with greater reactivity for the latter. 相似文献
875.
We construct a rigid-body (five-dimensional) potential-energy surface for the water-hydrogen complex using scaled perturbation theory (SPT). An analytic fit of this surface is obtained, and, using this, two minima are found. The global minimum has C2v symmetry, with the hydrogen molecule acting as a proton donor to the oxygen atom on water. A local minimum with Cs symmetry has the hydrogen molecule acting as a proton acceptor to one of the hydrogen atoms on water, where the OH bond and H2 are in a T-shaped configuration. The SPT global minimum is bound by 1097 microEh (Eh approximately 4.359744 x 10(-18) J). Our best estimate of the binding energy, from a complete basis set extrapolation of coupled-cluster calculations, is 1076.1 microEh. The fitted surface is used to calculate the second cross virial coefficient over a wide temperature range (100-3000 K). Three complementary methods are used to quantify quantum statistical mechanical effects that become significant at low temperatures. We compare our results with experimental data, which are available over a smaller temperature range (230-700 K). Generally good agreement is found, but the experimental data are subject to larger uncertainties. 相似文献
876.
Roberts RW 《Chemistry & biology》2004,11(11):1475-1476
Ostermeier, Guntas, and Mitchel describe a new approach to design enzymes that are allosterically regulated by an unrelated ligand . The resulting protein, constructed by nonhomologous recombination and genetic screens, displays switch-like behavior. 相似文献
877.
Kariuki NN Luo J Maye MM Hassan SA Menard T Naslund HR Lin Y Wang C Engelhard MH Zhong CJ 《Langmuir : the ACS journal of surfaces and colloids》2004,20(25):11240-11246
This paper reports findings of an investigation of the synthesis of monolayer-capped binary gold-silver (AuAg) bimetallic nanoparticles that is aimed at understanding the control factors governing the formation of the bimetallic compositions. The synthesis of alkanethiolate-capped AuAg nanoparticles was carried out using two related synthetic protocols using aqueous sodium borohydride as a reducing agent. One involves a two-phase reduction of AuCl(4)(-), which is dissolved in organic solution, and Ag(+), which is dissolved in aqueous solution. The other protocol involves a two-phase reduction of AuCl(4)(-) and AgBr(2)(-), both of which are dissolved in the same organic solution. AuAg nanoparticles of 2-3 nm core sizes with different compositions in the range of 0-100% Au have been synthesized. The two synthetic routes were compared in terms of bimetallic composition and size properties. Our new findings have allowed us to establish the correlation between synthetic feeding of metals and metal compositions in the bimetallic nanoparticles, which have important implications to the exploration of gold-based bimetallic nanoparticles for constructing sensing and catalytic nanomaterials. 相似文献
878.
R. Richard L. Hamer Danette Sekerak Richard C. Effland Joseph T. Klein 《Journal of heterocyclic chemistry》1988,25(3):991-994
The synthesis of the pyrrolo[1,2-b]cinnoline analogs 2 and 4–13 is described. The key step of this synthesis involves an intramolecular aromatic halide displacement on [2-(2-halobenzoyl)pyrrol-1-yl]carbamic acid esters. Several reactions of these cinnoline analogs with electrophilic reagents have been investigated. 相似文献
879.
Feichtinger Gustav Hartl Richard F. Kort Peter M. Seidl Andrea Wrzaczek Stefan 《Journal of Optimization Theory and Applications》2022,194(3):878-895
Journal of Optimization Theory and Applications - This paper considers a capital accumulation game where the installation costs of investments are lowered by the firm’s own capital stock... 相似文献
880.
This paper studies the optimal operation of an M/E k /1 queueing system with a removable service station under steady-state conditions. Analytic closed-form solutions of the controllable M/E k /1 queueing system are derived. This is a generalization of the controllable M/M/1, the ordinary M/E k /1, and the ordinary M/M/1 queueing systems in the literature. We prove that the probability that the service station is busy in the steady-state is equal to the traffic intensity. Following the construction of the expected cost function per unit time, we determine the optimal operating policy at minimum cost. 相似文献