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81.
Using a stereospecifically labelled precursor, the peroxide catalysed cyclisation of N--butyldihydrocinnamamide to the corresponding β-lactam was shown to proceed with complete loss of stereochemistry at the benzylic carbon atom. 相似文献
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Plaut DJ Martin SM Kjaer K Weygand MJ Lahav M Leiserowitz L Weissbuch I Ward MD 《Journal of the American Chemical Society》2003,125(51):15922-15934
Crystalline ternary inclusion monolayers consisting of a two-dimensional hydrogen-bonded host network of guanidinium (G) ions and organosulfonate (S) amphiphiles, and biphenylalkane guests, can be generated at the air-water interface through synergistic structural enforcement by hydrogen bonding and host-guest packing. Surface pressure-area isotherms of the 4'-hexadecylbiphenyl-4-sulfonate (C16BPS) amphiphile in the presence of G, with or without guest, are characterized by lift-off molecular areas expected for the GS sheet based on single-crystal X-ray structures of homologous bulk crystals. Intercalation of biphenylalkane guests (4-C(n)()H(2)(n)()(+1)-C(6)H(4)-C(6)H(5), n = 1, 4, 6, 10, 16; denoted CnBP) between organosulfonate hydrophobes, which define pocketlike cavities in the GS monolayer host, afford ternary inclusion monolayers with a 1:1 host-guest stoichiometry. These inclusion monolayers are less compressible than the guest-free host, consistent with dense packing of the biphenylalkane moieties of the host and the biphenylalkane guests. The inclusion monolayers are distinguished from the amorphous guest-free host and from selected guanidinium-free mixed monolayers by structural characterization with grazing-angle incidence X-ray diffraction (GIXD). The GIXD data for the ternary (G)C16BPS:C16BP and (G)C16BPS:C6BP inclusion monolayers obtained upon compression are consistent with a rectangular unit cell. The dimensions of these unit cells and refinement of the GIXD data suggest a "rotated shifted ribbon" GS hydrogen-bonding motif similar to that observed in some bulk GS crystals, including (G)(ethylbiphenylsulfonate). GIXD reveals that (G)C16BPS:C16BP and (G)C16BPS:C6BP are more crystalline than the corresponding guanidinium-free mixed monolayers. The (G)C16BPS:C6BP inclusion monolayer is stable upon compression, even though the alkyl-alkyl host-guest interactions are reduced due to the shorter hexyl substituents of the guest, demonstrating an important reinforcing role for the hydrogen-bonded GS sheet. The structure of a C16BPS:tetracosane (C24) mixed monolayer is independent of G; the unit cell symmetry and dimensions suggest a structure governed by alkyl-alkane interactions that prohibit formation of a GS network. These results illustrate that the existence of ternary inclusion monolayers with an intact GS network requires guest molecules that are structurally homologous with the hydrophobes of the host, in this case biphenylalkanes. The observation of these inclusion compounds suggests an approach for introducing functional nonamphiphilic molecules to an air-water interface through inclusion in a well-defined host. 相似文献
89.
Aitala EM Amato S Anjos JC Appel JA Ashery D Banerjee S Bediaga I Blaylock G Bracker SB Burchat PR Burnstein RA Carter T Carvalho HS Copty NK Cremaldi LM Darling C Denisenko K Devmal S Fernandez A Fox GF Gagnon P Gobel C Gounder K Halling AM Herrera G Hurvits G James C Kasper PA Kwan S Langs DC Leslie J Lundberg B Magnin J Massafferri A MayTal-Beck S Meadows B de Mello Neto JR Mihalcea D Milburn RH de Miranda JM Napier A Nguyen A d'Oliveira AB O'Shaughnessy K Peng KC Perera LP Purohit MV 《Physical review letters》2001,86(5):770-774
From a sample of 1172 +/- 61 D(+)-->pi(-)pi(+)pi(+) decays, we find gamma(D(+)-->pi(-)pi(+)pi(+))/gamma(D(+)-->K-pi(+)pi(+)) = 0.0311 +/- 0.0018(+0.0016)(-0.0026). Using a coherent amplitude analysis to fit the Dalitz plot of these decays, we find strong evidence that a scalar resonance of mass 478(+24)(-23) +/- 17 MeV/c(2) and width 324(+42)(-40) +/- 21 MeV/c(2) accounts for approximately half of all decays. 相似文献
90.
Miller SA Hiatt LA Keil RG Wright DW Cliffel DE 《Analytical and bioanalytical chemistry》2011,399(3):1021-1029
Immunoassays are important tools for the rapid detection and identification of pathogens, both clinically and in the research
laboratory. An immunoassay with the potential for the detection of influenza was developed and tested using hemagglutinin
(HA), a commonly studied glycoprotein found on the surface of influenza virions. Gold nanoparticles were synthesized, which
present multiple peptide epitopes, including the HA epitope, in order to increase the gravimetric response achieved with the
use of a QCM immunosensor for influenza. Specifically, epitopes associated with HA and FLAG peptides were affixed to gold
nanoparticles by a six-mer PEG spacer between the epitope and the terminal cysteine. The PEG spacer was shown to enhance the
probability for interaction with antibodies by increasing the distance the epitope extends from the gold surface. These nanoparticles
were characterized using thermogravimetric analysis, transmission electron microscopy, matrix-assisted laser desorption/ionization-time
of flight, and 1H nuclear magnetic resonance analysis. Anti-FLAG and anti-HA antibodies were adhered to the surface of a QCM, and the response
of each antibody upon exposure to HA, FLAG, and dual functionalized nanoparticles was compared with binding of Au–tiopronin
nanoparticles and H5 HA proteins from influenza virus (H5N1). Results demonstrate that the immunoassay was capable of differentiating
between nanoparticles presenting orthogonal epitopes in real-time with minimal nonspecific binding. The detection of H5 HA
protein demonstrates the logical extension of using these nanoparticle mimics as a safe positive control in the detection
of influenza, making this a vital step in improving influenza detection methodology. 相似文献