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31.
A laser flash photolysis study of the spectral properties and beta-scission reactions of a series of ring-substituted cumyloxyl radicals has been carried out. All cumyloxyl radicals display a broad absorption band in the visible region of the spectrum, which decays on the microsecond time scale, leading to a strong increase in absorption in the UV region of the spectrum, which is attributed to the corresponding acetophenone formed after beta-scission of the cumyloxyl radicals. The position of the visible absorption band is red-shifted by the presence of electron-donating ring substituents, while a blue-shift is observed in the presence of electron-withdrawing ring substituents, suggesting that + R ring substituents promote charge separation in the excited cumyloxyl radical through stabilization of the partial positive charge on the aromatic ring of an incipient radical zwitterion. Along this line, an excellent Hammett-type correlation between the experimentally measured energies at the visible absorption maxima of the cumyloxyl radicals and sigma(+) substituent constants is obtained. A red-shift is also observed on going from MeCN to MeCN/H(2)O for all cumyloxyl radicals, pointing toward a specific effect of water. The ring substitution does not influence to a significant extent the rate constants for beta-scission of the cumyloxyl radicals, which varies between 7.1 x 10(5) and 1.1 x 10(6) s(-1), a result that suggests that cumyloxyl radical beta-scission is not governed by the stability of the resulting acetophenone. Finally, k(beta) increases on going from MeCN to the more polar MeCN/H(2)O 1:1 for all cumyloxyl radicals, an observation that reflects the increased stabilization of the transition state for beta-scission through increased solvation of the incipient acetophenone product. 相似文献
32.
Mordini A Sbaragli L Valacchi M Russo F Reginato G 《Chemical communications (Cambridge, England)》2002,(7):778-779
Aziridinyl ethers are selectively and easily converted to either amino vinyl ethers or alkoxy allylamines by treatment with mixed metal bases (superbases). 相似文献
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Antonello?Vicenzo Michela?Rea Luca?Vonella Massimiliano?Bestetti Pietro?Luigi?CavallottiEmail author 《Journal of Solid State Electrochemistry》2004,8(3):159-166
In the present work the electrochemical deposition of Au-Sn alloys is addressed and a cyanide-free process is presented. The electrolyte is an acidic thiourea solution containing gold as a Au[CS(NH2)2]+ complex and tin as stannous ions. Results concerning the plating process development and deposit characterization are reported. Au-Sn alloy films with a Sn content up to 50 at% and a single-phase structure can be obtained from the acidic thiourea–Au(I) solution under pulsed current plating conditions. Alloy deposits show three main crystal structures: a face centred cubic (fcc) Au(Sn) solid solution, extending up to 7 at% Sn; a hexagonal close-packed structure, of the same type as the metallurgical phase, up to about 18 at% Sn; and a NiAs-type structure, corresponding to the phase of the equilibrium diagram, with an enlarged homogeneity range. Mechanical properties of thin layers of Au-Sn alloys derived from micro-indentation measurements follow the structural modification with the alloy composition. The ordered intermetallic phases occurring in the equilibrium binary system, in particular the and phases at 8 at% and 16 at% Sn, respectively, are not detected in the electrodeposited alloys. The main factors controlling electrochemical phase formation are pointed out, considering the differences between the phase structure of the electrodeposited alloys and the equilibrium phase diagram.Presented at the 3rd International Symposium on Electrochemical Processing of Tailored Materials held at the 53rd Annual Meeting of the International Society of Electrochemistry, 15–20 September 2002, Düsseldorf, Germany 相似文献
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A theory of the local magnetic response of a nonmagnetic impurity in a doped antiferromagnet, as relevant to the normal-state in cuprates, is presented. It is based on the assumption of the overdamped collective mode in the bulk system and on the evidence that equal-time spin correlations are only weakly renormalized in the vicinity of the impurity. The theory relates the Kondo-like behavior of the local susceptibility to the anomalous temperature dependence of the bulk magnetic susceptibility. 相似文献
36.
Stefan Eibl Andrew Fitch Michela Brunelli Alexander Dominic Evans Philip Pattison Marie Plazanet Mark Robert Johnson Christiane Alba‐Simionesco Helmut Schober 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(6):o278-o280
The title compound, C10H18, a decalin stereoisomer, crystallizes with Z′ = 0.5 in the space group P21/n. The trans‐decalin molecule is located on an inversion centre with both rings in a chair conformation, making for a quasi‐flat overall shape. Despite the absence of hydrogen bonds, it crystallizes easily. In this work the unknown crystal structure of trans‐decalin has been solved and refined using X‐ray powder diffraction data. 相似文献
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A general synthetic route allowing access to several spirocyclic N-carbethoxy-azabicyclo[3.2.1]octanones is developed. These novel ketones efficiently catalyse alkene epoxidation using Oxone® with up to 91.5% ee. 相似文献