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81.
82.
The reaction \documentclass{article}\pagestyle{empty}\begin{document}${\rm Br} + {\rm CH}_3 {\rm CHO}\buildrel1\over\rightarrow{\rm HBr} + {\rm CH}_3 {\rm CO}$\end{document} has been studied by VLPR at 300 K. We find k1 = 2.1 × 1012 cm3/mol s in excellent agreement with independent measurements from photolysis studies. Combining this value with known thermodynamic data gives k-1 = 1 × 1010 cm3/mol s. Observations of mass 42 expected from ketene suggest a rapid secondary reaction: in which step 2 is shown to be rate limiting under VLPR conditions and k2 is estimated at 1012.6 cm3/mol s from recent theoretical models for radical recombination. It is also shown that 0 ? E1 ? 1.4 kcal/mol using theoretical models for calculation of A1 and is probably closer to the lower limit. Reaction ?1 is negligible under conditions used. 相似文献
83.
In the reactions of 4,4-dimethylcyclohexadienylidene no evidence for cyclopropene formation has been found. By contrast, 4,4-dimethyl-4-silacyclohexadienylidene yields a product on reaction with butadiene that is best rationalized by intramolecular cyclopropene formation. 相似文献
84.
The high-pressure absolute rate constants for the decomposition of nitrosobenzene and pentafluoronitrosobenzene were determined using the very-low-pressure pyrolysis (VLPP) technique. Bond dissociation energies of DH0(C6H5? NO) = 51.5 ± 1 kcal/mole and DH0 (C6F5? NO) = 50.5 ± 1 kcal/mole could be deduced if the radical combination rate constant is set at log kr(M?1·sec?1) = 10.0 ± 0.5 for both systems and the activation energy for combination is taken as 0 kcal/mole at 298°K. δHf0(C6H5NO), δHf0(C6F5NO), and δHf0(C6F5) could be estimated from our kinetic data and group additivity. The values are 48.1 ± 1, –160 ± 2, and – 130.9 ± 2 kcal/mole, respectively. C–X bond dissociation energies of several perfluorinated phenyl compounds, DH0(C6F5–X), were obtained from the reported values of δHf0(C6F5X) and our estimated δHf0(C6F5) [X = H, CH3, NO, Cl, F, CF3, I, and OH]. 相似文献
85.
P. C. Painter B. A. Brozoski M. M. Coleman 《Journal of Polymer Science.Polymer Physics》1982,20(6):1069-1080
A systematic study of the sodium and calcium salts of an ethylene–methacrylic acid copolymer is reported. Fourier-transform infrared spectroscopy (in the midinfrared region) is applied to the characterization of structural changes as a function of temperature and time of annealing. In the spectra of calcium ionomers, bands associated with carboxylate dimers are identified and assignments of specific spectral features to multiplets and clusters are discussed. The spectroscopic changes observed in the spectra of sodium ionomers differ somewhat from their calcium counterparts in that a single infrared band attributed to isolated carboxylate groups is observed. Assignments of specific bands to multiplets and clusters can, however, be made in a manner consistent with the interpretation of the spectra of calcium ionomers. 相似文献
86.
87.
[reaction: see text] The synthesis of the naturally occurring kaempferol glycoside SL0101 has been accomplished, as has its biochemical evaluation. SL0101 exhibits selective and potent p90 Rsk inhibitory activity at nanomolar concentrations without inhibiting the function of upstream kinases such as MEK, Raf, or PKC. The synthesis verified the structural assignment of the natural product and has provided access to material sufficient for detailed biological evaluation. 相似文献
88.
We interpret the recent observation of a zero-bias anomaly in spin-1 quantum dots in terms of an underscreened Kondo effect. Although spin-1 quantum dots are expected to undergo a two-stage quenching effect, in practice the log-normal distribution of Kondo temperatures leads to a broad temperature region dominated by underscreened Kondo physics. General arguments, based on the asymptotic decoupling between the partially screened moment and the leads, predict a singular temperature and voltage dependence of the conductance G and differential conductance g, resulting in dg/dT approximately 1/T and dG/dV approximately 1/V. Using a Schwinger boson approach, we show how these qualitative expectations are borne out in a detailed many body calculation. 相似文献
89.
We report the first atomistic determination of the minimum energy path for a series of bond ruptures to advance a crack front. Saddle-point configurations on (111) cleavage planes in Si reveal a steplike distribution of atomic displacements, implying a kink mechanism which is known to control dislocation mobility. Manifestations of lattice trapping and directional cleavage anisotropy are further elucidated. 相似文献
90.
Stavinsky AV Mikhailov KR Lednicky R Vlassov AV Adams G Ambrozewich P Anciant E Anghinolfi M Asavapibhop B Asryan G Audit G Auger T Avakian H Bagdasaryan H Ball JP Barrow S Batourine V Battaglieri M Beard K Bektasoglu M Bellis M Benmouna N Bianchi N Biselli AS Boiarinov S Bonner BE Bouchigny S Bradford R Branford D Brooks WK Burkert VD Butuceanu C Calarco JR Carman DS Cetina C Chen S Cole PL Cords D Coleman A Corvisiero P Crabb D Cummings JP Dashyan N Sanctis ED Vita RD Degtyarenko PV Denizli H 《Physical review letters》2004,93(19):192301
Two-proton correlations at small relative momentum q were studied in the eA(3He,4He,C,Fe)-->e(')ppX reaction at E(0)=4.46 GeV using the CLAS detector at Jefferson Lab. The enhancement of the correlation function at small q was found to be in accordance with theoretical expectations. Sizes of the emission region were extracted, and proved to be dependent on A and on the proton momentum. The size of the two-proton emission region for He was measured in eA reactions for the first time. 相似文献