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61.
Fabrizi de Biani F Ienco A Laschi F Leoni P Marchetti F Marchetti L Mealli C Zanello P 《Journal of the American Chemical Society》2005,127(9):3076-3089
The reaction between equimolar amounts of Pt(3)(mu-PBu(t)()(2))(3)(H)(CO)(2), Pt(3)()H, and CF(3)SO(3)H under CO atmosphere affords the triangular species [Pt(3)(mu-PBu(t)()(2))(3)(CO)(3)]X, [Pt(3)()(CO)(3)()(+)()]X (X = CF(3)SO(3)(-)), characterized by X-ray crystallography, or in an excess of acid, [Pt(6)(mu-PBu(t)()(2))(4)(CO)(6)]X(2), [Pt(6)()(2+)()]X(2)(). Structural determination shows the latter to be a rare hexanuclear cluster with a Pt(4) tetrahedral core formed by joining the unbridged sides of two orthogonal Pt(3) triangles. The dication Pt(6)()(2+)() features also extensive redox properties as it undergoes two reversible one-electron reductions to the congeners [Pt(6)(mu-PBu(t)()(2))(4)(CO)(6)](+) (Pt(6)()(+)(), E(1/2) = -0.27 V) and Pt(6)(mu-PBu(t)()(2))(4)(CO)(6) (Pt(6)(), E(1/2) = -0.54 V) and a further quasi-reversible two-electron reduction to the unstable dianion Pt(6)()(2)()(-)() (E(1/2) = -1.72 V). The stable radical (Pt(6)()(+)()) and diamagnetic (Pt(6)()) species are also formed via chemical methods by using 1 or 2 equiv of Cp(2)Co, respectively; further reduction of Pt(6)()(2+)() causes fast decomposition. The chloride derivatives [Pt(6)(mu-PBu(t)()(2))(4)(CO)(5)Cl]X, (Pt(6)()Cl(+)())X, and Pt(6)(mu-PBu(t)()(2))(4)(CO)(4)Cl(2), Pt(6)()Cl(2)(), observed as side-products in some electrochemical experiments, were prepared independently. The reaction leading to Pt(3)()(CO)(3)()(+)() has been analyzed with DFT methods, and identification of key intermediates allows outlining the reaction mechanism. Moreover, calculations for the whole series Pt(6)()(2+)() --> Pt(6)()(2)()(-)()( )()afford the otherwise unknown structures of the reduced derivatives. While the primary geometry is maintained by increasing electron population, the system undergoes progressive and concerted out-of-plane rotation of the four phosphido bridges (from D(2)(d)() to D(2) symmetry). The bonding at the central Pt(4) tetrahedron of the hexanuclear clusters (an example of 4c-2e(-) inorganic tetrahedral aromaticity in Pt(6)()(2+)()) is explained in simple MO terms. 相似文献
62.
María D. Hernández-Alonso Juan M. Coronado Javier Soria José Carlos Conesa Vittorio Loddo Maurizio Addamo Vincenzo Augugliaro 《Research on Chemical Intermediates》2007,33(3-5):205-224
Oxidation of free cyanide in aqueous suspensions of three commercial TiO2 specimens, with different anatase crystal size, has been carried out in a batch photoreactor by simultaneously applying ozonation and photocatalysis. Dissolved ozone participates both in homogeneous and catalytic reactions with cyanide; the extents of these two processes are comparable to that of the photodegradation with oxygen. The reactivity results are well described by the Langmuir-Hinshelwood kinetic model, providing the values of the kinetic and equilibrium adsorption constants for the catalytic and photocatalytic reactions contributing to cyanide oxidation. The cyanide concentration decreases faster with time for catalysts with increasing anatase crystal size, being more marked under UV irradiation. EPR studies on gaseous ozone adsorption on the three samples in the dark have shown stronger ozone interactions with Ti4+ and O2? ions of the samples with largest anatase crystal size, leading to the formation of significant signals of Ti3+ and s O??O2 radicals than with the anatase with the lowest crystal size, where ozone was mainly adsorbed on water molecular arrangements covering its surface. The hampering of the ozone and/or cyanide adsorption by the water molecular arrangements covering the surface of the catalyst with the lowest crystal size would justify the low cyanide degradation rate observed for this sample. 相似文献
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This paper concerns with a state of bending for a linear transversely isotropic plate model based on the Mindlin assumption on the displacement. By using appropriate families of line-integral measures, we are able to establish results about the spatial behaviour of transient and steady-state solutions. All the results are obtained under relaxed hypotheses on the positive definiteness of the elasticity tensor. 相似文献
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68.
Frank Roschangar Jianxiu Liu Marine Dufour Vittorio Farina Azad Hossain Heewon Lee Richard Varsolona Pierre Beaulieu Chris H. Senanayake 《Tetrahedron letters》2008,49(2):363-366
A regioselective Larock approach to 3-substituted-2-pyridin-2-ylindoles from 2-alkynylpyridines and 2-iodoanilines is described herein. The unexpectedly high regioselectivity can be rationalized by a combination of steric, coordinative and electronic effects. 相似文献
69.
A variable neighborhood search for the capacitated arc routing problem with intermediate facilities 总被引:2,自引:0,他引:2
Michael Polacek Karl F. Doerner Richard F. Hartl Vittorio Maniezzo 《Journal of Heuristics》2008,14(5):405-423
The capacitated arc routing problem (CARP) focuses on servicing edges of an undirected network graph. A wide spectrum of applications
like mail delivery, waste collection or street maintenance outlines the relevance of this problem. A realistic variant of
the CARP arises from the need of intermediate facilities (IFs) to load up or unload the service vehicle and from tour length
restrictions. The proposed Variable Neighborhood Search (VNS) is a simple and robust solution technique which tackles the
basic problem as well as its extensions. The VNS shows excellent results on four different benchmark sets. Particularly, for
all 120 instances the best known solution could be found and in 71 cases a new best solution was achieved. 相似文献
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