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71.
H. Pongratz K. K. Mayer W. Wiegrebe 《Monatshefte für Chemie / Chemical Monthly》1997,128(6-7):659-673
Summary N-Butoxy- and N-propoxy-imines derived fromo-,m-, andp-substituted benzaldehydes (X = F, Cl, Br, I) decompose upon electron impact to the respective aldoximes by loss of C
n
H2n
and competitivelyvia 1,5-distonic radical cations by loss of CH2O to 1,3-distonic ions which eliminate H and/or a halogen atom in the course of homolytic aromatic substitution, giving rise to cyclic (M-CH2O-H)+ or (M-CH2O-X
)+ ions.Dedicated with warm regards to Prof. Dr.D. Seebach, Zürich, on the occasion of his 60th birthday 相似文献
72.
A. A. Vedenyapin M. D. Baturova G. I. Ioseliani G. Kh. Areshidze 《Russian Chemical Bulletin》1997,46(1):76-80
The anodic oxidation of the carbon felt Carbonetcalon results in the formation of surface defects which serve as centers of
strong adsorption of PdII, NiII, and CuII ions. The electrochemical reduction of adsorbed ions makes it possible to obtain metallic catalysts, which undergo multiple
redox cycles without loss of metal. The catalysts are characterized by high dispersity of the reduced phase, high adsorption
capacity with respect to hydrogen, and 100% selectivity in hydrogenation of acetophenone.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 81–85, January 1997 相似文献
73.
G. Papanastasiou A. Papoutsis M. Tsirtou I. Ziogas 《Journal of solution chemistry》1996,25(2):203-217
The kinetics of the reaction between sodium ethoxide and methyl iodide has been studied at 25°C in various cyclohexane-ethanol solvent mixtures with a cyclohexane content of 10 to 50% per volume. The determination of the rate constants att=0 were carried out by a new iterative method proposed in this investigation. The obtained results show that the reaction rate decreases with the increasing cyclohexane content. This behavior can be attributed to various solute-solvent interactions of electrostatic nature. On the other hand, the variation of ion and ion pairs rate constants with solvent composition permits the various solvation effects to be taken into account. 相似文献
74.
M. Y. El-Sheikh A. M. Habib A. K. Abou-Seif A. B. Zaki 《Journal of inclusion phenomena and macrocyclic chemistry》1986,4(4):359-367
The kinetics of the decomposition of hydrogen peroxide was studied in aqueous medium in the temperature range 25–40°C in the presence of Wofatit KPS-resin in the form of Cu(II)-ammine complex ions. The rate constant was deduced at various degrees of resin cross-linkage and different concentrations of hydrogen peroxide. The order of the decomposition reaction varied from first order to half order, i.e., the order of the reaction decreased with increasing the concentration of H2O2. The decomposition process was found to be a catalytic reaction which was controlled by the chemical reaction of H2O2 molecules with the active species inside the resin particles. The mechanism of the reaction can be summarized by the equation
in which the subsequent reactions of the probable active complex are discussed. 相似文献
75.
The results of kinetic studies on ligand substitution in [M3(CO)11X]– complexes (M = Ru, Os; X = Cl, Br, I) are summarized. The [Os3(CO)11X]– complexes react with PPh3 under mild conditions to initially yield monosubstituted products [Os3(CO)10(PPh3)X]–. The rate of CO substitution obeys a first-order equation with respect to the concentration of the complex and does not depend on the ligand concentration. The rates of the reactions decrease in the order Cl > Br > I withH values increasing from 15 to 18 kcal mol–1 and S
values varying from –19 to –13 cal mol–1 K–1. The enhanced reactivities of these complexes as well as the low activation energies and negative activation entropies are discussed in terms of the effects of -X bridge formation on the transition state of the reaction. Reactions of PPN[Ru3(CO)11–x
(Cl)] (PPN is the bis(triphenylphosphine)iminium cation;x=0, 1) and PPN[Ru3(CO)9(3-I)] with alkynes are also reported. The reactivities of alkynes follow the order BuCCH PhCCH EtCCEt PhCCPh. The higher rates of the reactions of monosubstituted acetylenes compared with those of their disubstituted analogs are explained by agostic interaction between the metal atom and the C-H bond in the reaction transition state and by steric effects. The results obtained attest that the reaction with alkynes occursvia intermediates containing halide bridges and that 3-halide complexes are more reactive than 2-halide complexes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1540–1545, September, 1994.This work was supported by a Presidential Grant from Northwestern University. One of the authors (F. Basolo) wishes to thank Academician M. E. Vol'pin for the invitation to participate in the Workshop The Modern Problems of Organometallic Chemistry (INEOS-94) and Academician O. M. Nefedov for the invitation to publish a review in theRussian Chemical Bulletin. 相似文献
76.
Polymer enhanced ultrafiltration (PEUF) is a newly developed method for the removal of heavy metals from aqueous solutions. This method was applied for the removal of mercury and cadmium with the presence of polyethyleneimine (PEI) as a water soluble polymer. After ultrafiltration experiments for metal–polymer mixtures, two separate streams, namely, retentate and permeate, former of which contains mainly metal–polymer complex and free polymer molecules while latter of which mainly contains free metal ions, were obtained. At the end of PEUF experiments, performance of operation was determined by concentration analyses which was achieved by atomic absorption spectroscopy (AAS) applied in a different way for permeate and retentate streams considering the effect of presence of polymer. For mercury analysis, cold vapor AAS was applied. It was observed that the presence of PEI did not affect the atomic absorption signal when 10% HCl was added to the sample solutions. For calcium and cadmium, flame AAS was used. It was observed that change in PEI concentration results in change in measured concentration of calcium and cadmium. Therefore, two new approaches were developed for accurate measurement of concentrations of calcium and cadmium. It was also observed that presence of other metals did not affect the accuracy of the measurement of a particular metal in the concentration range studied. 相似文献
77.
78.
气相二茂铁双电荷离子的动能谱研究 总被引:1,自引:0,他引:1
The unimolecular charge separation reactions of the doubly charged ions FeC_(10)H_(10)~(2+)、FeC_(10)H_9~(2+)、FeC_(10)H_8~(2+) produced in the ion source by electron impact from ferrocene have been studied using Mass analyzed Ion Kinetic Energy Spectrometry (MIKES) technique. From the values of the kinetic energy releases (T), the intercharge distances (R) of the exploding doubly charged ions in their transition structures have been estimated and some structural informations about the transition states can be obtained. The collision induced reactions of the FeC_(10)H_(10)~(2+) ion with Ar have been studied using MIKES, we postulate a new type of continuing reaction which may be "collisional charge separation induced dissociation". 相似文献
79.
Simanenko Yu. S. Popov A. F. Prokop'eva T. M. 《Theoretical and Experimental Chemistry》2003,39(5):288-295
Among hydroxamate ions (typical nucleophiles), anomalously high nucleophilicity relative to 4-nitrophenyl diethyl phosphonate is seen in anions which have general basic catalytic sites that provide anchimeric assistance for proton transfer in the transition state. 相似文献
80.
A. Kolker L. P. S. Safonova A. N. Kinchin G. A. Krestov 《Journal of solution chemistry》1990,19(10):975-994
Experimentally determined are the enthalpies of solution of 12 electrolytes (LiBr, LiI, NaBr, NaI, NaBPh4, Et4NCl, Et4NBr, Pr4Br, Bu4NBr, Am4NBr, Ph4PCl, Ph4PBr) in ethanol at –50 to 55°C. sHo values obtained on the basis of four different extrapolation equations are analyzed. The effect of temperature changes on the thermodynamic parameters of solvation indindividual ions are calculated using thermodynamic data for the salt crystals (lattice) with the assumption that solvC
p
o
(Ph4P+)=solvC
p
o
(Ph4P-). 相似文献