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121.
γ‐Halocarbanions, short‐lived intermediates, add to electron‐deficient double bonds of aldehydes, Michael acceptors, and imines to form anionic adducts that enter intramolecular 1,5‐substitution to form five‐membered rings of tetrahydrofurans, cyclopentanes, and pyrrolidines, respectively. Although the γ‐halocarbanions can be generated by simple deprotonation of appropriate precursors, a wealth of other methods based on Lewis acid‐catalyzed opening of cyclopropanes with formation of dipolar species utilizes a similar mechanistic scheme. In our review, we analyze kinetic relations of elementary processes in the multistep transformations, and demonstrate how structural factors influence the mechanisms and selectivity of the reaction. 相似文献
122.
The paper develops a technique for proving properties that are typical in the boundary of the connectedness locus with respect
to the harmonic measure. A typical expansion condition along the critical orbit is proved. This condition implies a number
of properties, including the Collet-Eckmann condition, Hausdorff dimension less than 2 for the Julia set, and the radial continuity
in the parameter space of the Hausdorff dimensions of totally disconnected Julia sets.
Oblatum 6-XI-1998 & 12-V-2000?Published online: 11 October 2000 相似文献
123.
P. Solarz M. Nikl A. Kos R. Lisiecki W. Ryba‐Romanowski A. Rzepka S. Ganschow A. Pajczkowska 《Crystal Research and Technology》2007,42(12):1308-1313
Single crystals of GdCa4O(BO3)3 (GdCOB) pure and doped with Eu concentration of 1 and 4 at% were grown by the Czochralski and micropulling‐down methods. The distribution of Eu ions in GdCOB crystals was uniform. The substitutions of Eu3+ in Gd, Ca(1) and Ca(2) cation sites and eventually formation Eu2+ have been investigated. The spectroscopic properties of crystals are compared with the properties of nanopowders obtained by sol‐gel method. Radioluminescence spectra of undoped GdCOB crystal show the characteristic emission of Gd3+ at about 312 nm, whereas this emission dramatically decreases in Eu‐doped crystals upon X‐ray excitation, as well as in Eu‐doped nanopowders excited in vacuum ultraviolet (VUV) region. The VUV excitation in the range 125‐333 nm for Eu‐doped samples leads to strong emission in red coming from the 5D0 multiplet of Eu3+, only. In the photoluminescence decay kinetics of 312 nm emissions substantial shortening and departure for single exponential decay in Eu‐doped samples is clearly observed. Higher Eu doping results in further acceleration of the decay. In undoped GdCOB crystal, the lifetime of the Gd3+ 6P7/2 multiplet is 2.79 ms. The Eu3+ 5D0 decay kinetics monitored at 613 nm are rather constant. Numerical fitting of fully exponential curves, reveals lifetimes 2.7 ms for nanopowder and 2.5 ms for single crystal. The results suggest that this material may be used as a red phosphor in plasma display panels in nanopowder form because of strong excitation band of Eu3+ luminescence in the 160‐200 nm regions. Contrary to nanopowder sample, such an excitation band, attributed to the Gd3+–O2– charge transfer was not observed in crystal obtained by the micropulling‐down method. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
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Lipophilicity study of eight cephalosporins by reversed‐phase thin‐layer chromatographic method 下载免费PDF全文
Monika Dąbrowska Łukasz Komsta Jan Krzek Kinga Kokoszka 《Biomedical chromatography : BMC》2015,29(11):1759-1768
The lipophilicity (RM0) and specific hydrophobic surface area for the representatives of four generation cephalosporins have been determined by reversed‐phase thin‐layer chromatography, and the effect of different mobile‐phase modifiers (such as methanol, acetonitrile, acetone, 1,4‐dioxane and 2‐propanol) on the retention has been studied. The compounds studied showed typical retention behavior; their RM values decreased linearly with increasing concentration of the organic modifier in the eluent. The linear correlations between the volume fraction of the organic solvent and the RM values over a limited range were established for each solute, resulting in high values of correlation coefficients (>0.95 in most cases). RM values were determined by various concentrations of organic modifier, and the correlation obtained was extrapolated to 0% of organic modifier. Chromatographically established logP (RM0) parameters were compared with computationally calculated partition coefficients values (AClogP, ALOGP, KOWWIN, ALOGPs, XLOGP2, MLOGP and XLOGP3) and experimental octanol–water logP values (measured by the shake flask method). The received results demonstrate that RP‐TLC may be a good alternative technique for analytics in describing the lipophilic nature of investigated cephalosporins as well as the activity. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
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