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101.
F. David-Quillot A. Duchêne J.-M. Catala A. Balland-Longeau J. Thibonnet 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(5):461-467
Fourteenth group oganometallic styrene derivatives were synthesised by nitroxide-mediated controlled radical polymerization using di-tert butyl nitroxide (A-T) as initiator. This is the first time that nitroxide-controlled radical polymerization has been successfully adapted for the synthesis of new polystyrenes bearing organometallic species with controlled molecular weights and narrow polydispersities. Monomer reactivity ratios were determined in controlled nitroxide-mediated radical copolymerization between styrene and substituted styrene. All experiments permitted the synthesis of new organometallic polymers that will be used for the development of a polymer capsule for Inertial Confinement Fusion Experiments. 相似文献
102.
We show that the Chern character of a variation of polarized Hodge structures of weight one with nilpotent residues at dies up to torsion in the Chow ring, except in codimension 0. 相似文献
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104.
Os(H)(3)ClL(2) (L = P(i)Pr(3)) reacts at 20 degrees C with vinyl fluoride in the time of mixing to produce OsHFCl([triple bond]CCH(3))L(2) and H(2). In a competitive reaction, the liberated H(2) converts vinyl fluoride to C(2)H(4) and HF in a reaction catalyzed by Os(H)(3)ClL(2). A variable-temperature NMR study reveals these reactions proceed through the common intermediate OsHCl(H(2))(H(2)C=CHF)L(2), via OsClF(=CHMe)L(2) and OsHCl(H(2))(C(2)H(4))L(2), all of which are detected. DFT(B3PW91) calculations of the potential energy and free energy at 298 K of possible intermediates show the importance of entropy to account for their thermodynamic accessibility. Calculations of unimolecular C-F cleavage of coordinated C(2)H(3)F confirms the high activation energy of this process. Catalysis by HF is thus suggested to account for the fast observed reactions, and scavenging of HF with NEt(3) changes the product to exclusively Os(H)(2)Cl(CCH(3))L(2). The analogous reaction of Os(H)(3)ClL(2) with H(2)C=CF(2) produces exclusively OsHFCl(=CCH(3))L(2) and HF, and the latter is again suggested to catalyze C-F scission via the observed intermediates Os(H)(2)Cl(CF(2)CH(3))L(2) and OsHCl(=CFMe)L(2). 相似文献
105.
Baer AJ Koivisto BD Côté AP Taylor NJ Hanan GS Nierengarten H Van Dorsselaer A 《Inorganic chemistry》2002,41(20):4987-4989
Diplatinum metalloreceptors anti-4a and anti-4b exhibit dynamic behavior in solution that is modified by anion binding. An X-ray crystal structure determination of anti-4a supports its proposed solution structure. 相似文献
106.
An unprecedented surface oxidation of polystyrene substrates by wet chemistry under basic conditions
Hambardzumyan A Biltresse S Dufrêne Y Marchand-Brynaert J 《Journal of colloid and interface science》2002,252(2):443-449
The surface of polystyrene substrates has been modified by wet chemistry consisting of a treatment with sodium hydroxide in a water-methanol solution at 50 degrees C for 15 h, under air atmosphere. The resulting samples were analyzed by XPS and AFM. The surface functional groups (hydroxyl and carboxyl functions) were assayed by radiolabeling. All the results are consistent with a surface oxidation process. 相似文献
107.
Nierengarten H Leize E Breuning E Garcia A Romero-Salguero F Rojo J Lehn JM Van Dorsselaer A 《Journal of mass spectrometry : JMS》2002,37(1):56-62
The self-assembly of the terdentate ligands 1a-h, based on terpyridine-like binding sites, with octahedrally coordinated metal ions, such as Fe(II), Co(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II), leads to the formation of the supramolecular grid-type complexes 2a-c(M(II)), 3d-g(M(II)) and 4h(M(II)). The structures and compositions of these coordination complexes in solution were deduced from electrospray mass spectrometry (ESMS) measurements. The results agree with the data available from x-ray radiocrystallography in the solid state and/or NMR spectroscopy in solution. ESMS may be applied in cases where other methods are difficult to use or inconclusive. This study stresses the power of ESMS in supramolecular chemistry. 相似文献
108.
109.
110.
Three-dimensional microfabrication by two-photon-initiated polymerization with a low-cost microlaser 总被引:3,自引:0,他引:3
Fabrication of submicrometer structures by two-photon-initiated polymerization is performed with an inexpensive and low-power microlaser. This is made possible by the design of photoinitiators with strong two-photon absorption cross sections. We analyze the influence of both material properties and irradiation conditions on the two-photon polymerization rate and show that resins based on our highly sensitive two-photon photoinitiator can be solidified with microlaser excitation, whereas commercial UV photoresins require ultrashort and intense laser pulses. 相似文献