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排序方式: 共有1239条查询结果,搜索用时 31 毫秒
31.
Retbøll M Edwards AJ Rae AD Willis AC Bennett MA Wenger E 《Journal of the American Chemical Society》2002,124(28):8348-8360
A series of nickel(II) and palladium(II) aryl complexes substituted in the ortho position of the aromatic ring by a (pinacolato)boronic ester group, [MBr[o-C(6)H(4)B(pin)]L(2)] (M = Ni, L(2) = 2PPh(3) (2a), 2PCy(3) (2b), 2PEt(3) (2c), dcpe (2d), dppe (2e), and dppb (2f); M = Pd, L(2) = 2PPh(3) (3a), 2PCy(3) (3b), and dcpe (3d)), has been prepared. Many of these complexes react readily with KO(t)Bu to form the corresponding benzyne complexes [M(eta(2)-C(6)H(4))L(2)] (M = Ni, L(2) = 2PPh(3) (4a), 2PCy(3) (4b), 2PEt(3) (4c), dcpe (4d); M = Pd, L(2) = 2PCy(3) (5b)). This reaction can be regarded as an intramolecular version of a Suzuki cross-coupling reaction, the driving force for which may be the steric interaction between the boronic ester group and the phosphine ligands present in the precursors 2 and 3. Complex 3d also reacts with KO(t)Bu, but in this case disproportionation of the initially formed eta(2)-C(6)H(4) complex (5d) leads to a 1:1 mixture of a novel dinuclear palladium(I) complex, [(dcpe)Pd(mu(2)-C(6)H(4))Pd(dcpe)] (6), and a 2,2'-biphenyldiyl complex, [Pd(2,2'-C(6)H(4)C(6)H(4))(dcpe)] (7d). Complexes 2a, 3b, 3d, 4b, 5b, 6, and 7d have been structurally characterized by X-ray diffraction; complex 5b is the first example of an isolated benzyne-palladium(0) species. 相似文献
32.
A gelatin matrix was simultaneously doped with nine equimolar, homologous, tetraalkylammonium salts ranging in mass from 210 to 700 Da. Bombardment of the sample with kiloelectronvolt ions resulted in a nonidentical distribution of relative cation intensities with a maximum at m/z 242 for samples with a total salt concentration of 0.004 g of salt/g of gelatin. A rapid increase in relative intensities with increasing mass is observed for the low mass salts and is believed to be linked to changes in the ionization efficiencies. The changes in ionization efficiencies are likely related to decreasing coulombic attractive forces between the organic cation and the counterion. Disappearance cross-sections, determined from decay curves, indicate that sputter-induced damage increases with increasing mass of the cation. Fragment-to-intact cation ratios also suggest that damage accumulates fastest in the heaviest salts. These observations indicate that desorption yields of the organic salts in a gelatin matrix decrease with increasing mass. In addition, suppression of lower mass tetraalkylammonium salt intact cation intensities was observed for salt-in-gelatin concentrations greater than 10−3 g/g. 相似文献
33.
A review with 136 references on the principles and recent developments in the solid-phase extraction based on polymer sorbents is presented. New polymer-based materials, chromatographic modes, experimental configurations are described and their advantages for a rapid sample preparation of certain classes of compounds with different functional groups are discussed and compared to silica-based sorbents. 相似文献
34.
T. Bennett D. Cavers J. M. D'Auria 《Journal of Radioanalytical and Nuclear Chemistry》1973,13(1):201-212
The purpose of this study was to demonstrate the versatility of combining the use of high resolution, Ge(Li) γ-detectors with
the techniques of fast neutron activation analysis. A compilation of γ-ray spectra are presented for irradiation of 30 elements
with 14.8 MeV neutrons under standard conditions and the origin of all major photopeaks is determined. 相似文献
35.
The response of a monoaza-15-crown-5 with an optically active aminobenzoxazinone moiety to divalent cations was investigated. The crown ether was found to undergo a strong emission shift to the blue when complexed with specific divalent metals that have ionic diameters between 1.9-2.4 A. Consequently the photoactive macrocycle is responsive to Mg(2+), Ca(2+), Ba(2+), Sr(2+), Cd(2+), and particularly responsive to Hg(2+)and Pb(2+). Macrocycle emission spectra are shown to be a function of cation concentration. Alkaline metal cations and smaller transition metals ions such as Ni(2+), Co(2+)and Zn(2+)do not cause significant changes in the macrocycle emission spectra. Emission, absorption, and complex stability constants are determined. Mechanisms of cation selectivity and spectral emission shifts are discussed. Challenges involving immobilization of the macrocycle while preserving its spectral response to cations are explored. 相似文献
36.
M. Jochum R. Bakry I. Wartusch C. W. Huck H. Engelhardt G. K. Bonn 《Chromatographia》2002,56(5-6):263-268
Summary This paper reports on the use of a polymer-based, strong anion-exchange stationary phase for rapid, selective and sensitive
analysis of physiological important mono-, di- and oligosaccharides by high-performance anion-exchange chromatography (HPAEC)
with pulsed amperometric detection (PAD) under alkaline conditions. The adsorbent was obtained by direct nitration of 3 and
5 μm, spherical non-porous highly cross-linked, styrene-divinylbenzene copolymer (PS-DVB) beads, followed by reduction of
superficially introduced nitro groups with nascent hydrogen and quaternization of the resultant amino groups with iodomethane.
Extended exposure to high pressure and strong alkaline conditions did not have any untoward effect on mechanical stability
and chromatographic performance. A comparison of the 3 and 5 μm beads showed, that the synthesized 3 μm highly cross-linked
PS-DVB particles are the preferred phases for the separation of monosaccharides and the 5 μm particles are preferable for
the separation of oligosaccharides. To demonstrate the suitability for the analysis of complex samples, the optimized and
validated system was used for the determination of glucose, fructose and sucrose in apple juice and other soft drinks such
as Coca Cola. Finally, analysis within a few minutes without sample pretreatment down to a lower limit of detection of 0.174–0.504
μg mL−1 at a linearity with R2>0.994 and a repooducibility higher than 98% further confirmed the efficiency of these polymeric sorbents. 相似文献
37.
Photolysis of the title compounds in acidic aqueous solution results in "activation" of the distal m-methyl group, resulting in deuterium exchange (Phi approximately 0.1) when D(2)O is used. The reaction is not observed in neutral aqueous solution or in deuterated organic solvents such as CD(3)CN. The reaction is best rationalized by a mechanism involving initial protonation at the carbonyl oxygen of the triplet excited state. [reaction: see text] 相似文献
38.
39.
Quantum cryptography using any two nonorthogonal states 总被引:6,自引:0,他引:6
Bennett CH 《Physical review letters》1992,68(21):3121-3124
40.
Quantum cryptography without Bell's theorem 总被引:2,自引:0,他引:2