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31.
Albert Theolier Agnès Choplin Lindora DOrnelas Jean-Marie Basset Gianmaria Zanderighi C. Sourisseau 《Polyhedron》1983,2(2):119-121
Ru3(CO)12, supported on silica in the absence of oxygen, reacts with silanol groups of the surface to produce a grafted cluster , which has been characterized by IR and Raman spectroscopy; the molecular formula of this cluster is in agreement with the stoichiometric balance of CO evolved during its formation from Ru3(CO)12. The grafted cluster is an intermediate step to produce by thermal decomposition small metallic ruthenium particles of 14 Å together with some Ru(II) carbonyl species encapsulated in the silica surface. 相似文献
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Nicolas Popoff Jeff Espinas Eric Gour Olivier Boyron Erwan Le Roux Jean‐Marie Basset Rgis M. Gauvin Aimery De Mallmann Mostafa Taoufik 《Macromolecular rapid communications》2011,32(23):1921-1924
Silica‐supported titanium(IV) chloride is readily reduced by Mashima and co‐workers' reagent (1‐methyl‐3,6‐bis(trimethylsilyl)‐1,4‐cyclohexadiene) to afford materials active in ethylene polymerisation without need of aluminum alkyl cocatalyst. 相似文献
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Leduc AM Salameh A Soulivong D Chabanas M Basset JM Copéret C Solans-Monfort X Clot E Eisenstein O Böhm VP Röper M 《Journal of the American Chemical Society》2008,130(19):6288-6297
The surface complex [([triple bond]SiO)Re([triple bond]CtBu)(=CHtBu)(CH2tBu)] (1) is a highly efficient propene metathesis catalyst with high initial activities and a good productivity. However, it undergoes a fast deactivation process with time on stream, which is first order in active sites and ethene. Noteworthy, 1-butene and pentenes, unexpected products in the metathesis of propene, are formed as primary products, in large amount relative to Re (>1 equiv/Re), showing that their formation is not associated with the formation of inactive species. DFT calculations on molecular model systems show that byproduct formation and deactivation start by a beta-H transfer trans to the weak sigma-donor ligand (siloxy) at the metallacyclobutane intermediate having a square-based pyramid geometry. This key step has an energy barrier slightly higher than that calculated for olefin metathesis. After beta-H transfer, the most accessible pathway is the insertion of ethene in the Re-H bond. The resulting pentacoordinated trisperhydrocarbyl complex rearranges via either (1) alpha-H abstraction yielding the unexpected 1-butene byproduct and the regeneration of the catalyst or (2) beta-H abstraction leading to degrafting. These deactivation and byproduct formation pathways are in full agreement with the experimental data. 相似文献
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Guillemot G Thieuleux C Copéret C Soulivong D Spitzmesser S Basset JM 《Dalton transactions (Cambridge, England : 2003)》2007,(40):4589-4593
Grafting the well-defined molecular complexes [(ArO)Zr(CH2tBu)3], , and [(ArO)2Zr(CH2tBu)2], , on SiO2-(700) (ArO=2,6-Ph2C6H3O) gives the corresponding monosiloxy surface complexes [([TRIPLE BOND]SiO)Zr(CH2tBu)2(OAr)] and [([TRIPLE BOND]SiO)Zr(CH2tBu)(OAr)2] as major surface species as evidenced by mass balance analysis, IR and NMR spectroscopies. In both cases, minor cyclometallated species (ca. 20%) are also probably formed during the grafting process. While /SiO2-(700) catalytically transforms propane into its lower and higher homologues, /SiO2-(700) remains inactive. Moreover, the formation of butane as the major higher homologues is consistent with the formation of metallocarbene intermediates in this system in contrast to what was observed for the corresponding homologation reaction on silica supported zirconium hydrides. 相似文献
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Cletus A D'Souza Vikramjit Chopra Richard Varhol Yuan-Yun Xie Slavita Bohacec Yongjun Zhao Lisa LC Lee Mikhail Bilenky Elodie Portales-Casamar An He Wyeth W Wasserman Daniel Goldowitz Marco A Marra Robert A Holt Elizabeth M Simpson Steven JM Jones 《BMC neuroscience》2008,9(1):1-14