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41.
Kurt V. Schenker Wolfgang Von Philipsborn C. Anderson Evans Werner Skuballa Georg-Alexander Hoyer 《Helvetica chimica acta》1986,69(7):1718-1727
The configurations of the 5,6-double bond in the carbacyclins iloprost ( 3 ; (E)) and isoiloprost ( 4 ; (Z)) are based on a complete assignment of the 13C and 1H resonances determined by 1D and 2D 13C-NMR and 1H-NMR methods. 相似文献
42.
Pop D Winter B Freyer W Widdra W Hertel IV 《The journal of physical chemistry. B》2005,109(16):7826-7833
Photoemission measurements were performed on a series of stepwise benzoannelated zinc porphyrazine molecules in thin films. The electronic structure of tert-butyl-substituted zinc tetraazaporphyrin, phthalocyanine, and naphthalocyanine is investigated using mainly EUV synchrotron radiation. A detailed analysis of the zinc satellites in the spectra of the valence region is performed in an attempt to infer the effect of ligand size extension on the metal-ligand interactions. No differences in the character of the bond between zinc and ligand were detected as a function of ligand size. The results are compared with those for the respective metal-free and copper-containing molecules. 相似文献
43.
Oleinikova A Smolin N Brovchenko I Geiger A Winter R 《The journal of physical chemistry. B》2005,109(5):1988-1998
The formation of spanning hydrogen-bonded water networks on protein surfaces by a percolation transition is closely connected with the onset of their biological activity. To analyze the structure of the hydration water at this important threshold, we performed the first computer simulation study of the percolation transition of water in a model protein powder and on the surface of a single protein molecule. The formation of an infinite water network in the protein powder occurs as a 2D percolation transition at a critical hydration level, which is close to the values observed experimentally. The formation of a spanning 2D water network on a single rigid protein molecule can be described by adapting the cluster analysis of conventional percolation studies to the characterization of the connectivity of the hydration water on the surface of finite objects. Strong fluctuations of the surface water network are observed close to the percolation threshold. Our simulations also furnish a microscopic picture for understanding the specific values of the experimentally observed hydration levels, where different steps of increasing mobility in the hydrated powder are observed. 相似文献
44.
45.
Viorica Lopez-Avila Richard Young Werner F. Beckert 《Journal of separation science》1997,20(9):487-492
This paper describes the extraction of 49 organophosphorus pesti-cides (OPPs) from water samples using solid-phase microextraction (SPME). Three fibers, including a 15-μm XAD-coated fiber, a 85-μm polyacrylate-coated fiber, and a 30-μm polydimethylsilox-ane-coated fiber (PDMS), were evaluated here. The effects of stirring and the addition of NaCl to the sample were examined for the polyacrylate-coated fiber. The precision of the technique was examined for all three fibers and the extraction kinetics were investigated using the XAD- and polyacrylate-coated fibers. With some exceptions, the XAD- and polyacrylate-coated fibers performed better than the PDMS-coated fiber. The superiority of the XAD-nd polyacrylate-coated fiber. The superiority of the XAD- and polyacrylate-coated fibers over the PDMS-coated fibers can be attribuibuted to the aromatic functionalities of the XAD and the polar functionalities in the polyacrylate. The relatively high percent RSDs indicate that the SPME technique needs to be further refined before it can be used for anything other than screening. A more effective form of agitation than mechanical stirring may be neccessary to reduce variability and achieve a faster equilibrium between the sample and the SPME fiber. 相似文献
46.
Clasine van Winter 《Integral Equations and Operator Theory》1987,10(1):96-139
This paper starts from a self-adjoint Schrödinger operator H(0) for three particles. If the interaction is dilation-analytic, H(0) has an analytic continuation H() (>0). G(t,) (–(±,a,) defined as strong limits, when t±, of t-dependent operators. The wave operators establish transformations under which the subgroups are similar to unitary groups. The scattering matrix determined by G(t,) is diagonal with respect to a.This work was supported in part by the National Science Foundation under grant DMS-8301096. 相似文献
47.
48.
[reaction: see text] The fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by nucleotides has been studied. The quenching mechanism was analyzed on the basis of deuterium isotope effects, tendencies for exciplex formation, and the quenching efficiency in the presence of a molecular container (cucurbit[7]uril). Exciplex-induced quenching appears to prevail for adenosine, cytidine, and uridine, while hydrogen abstraction becomes competitive for thymidine and guanosine. Compared to other fluorescent probes, DBO responds very selectively to the type of nucleotide. 相似文献
49.
The reaction of C5H5Rh(CO)(PiPr3) (1] which is prepared from C5H5Rh(CO)2 and neat P1Pr3, with the nitriloxides 2-RC6H4CNO (R = H, Cl) leads to the formation of the metallaheterocycles C5H5(P1Pr3)
) (2, 3) in 90–95% yield. Compound 1 reacts with tosylazide to give the C,N-bound isocyanate complex C5 H5(PiPr3)Rh(η2-TosN=C=O) (6). Analogously, on treatment of C5Me5Co(CO)(PMe3) with phenylazide the phenylisocyanate derivative C5Me5(PMe3)Co(η2-PhN=C=O) (7) is formed. Protonation of 7 with CF3CO 2H affords the non-ionic carbamoylcobalt complex C5Me5(PMe3)Co[C(O)NHPh](O2CCF3) (8). The X-ray structural analysis of 2 reveals the presence of an almost planar
heterocycle in which the two Rh-C distances differ by 0.045 Å 相似文献
50.
Five different structures of CH5
+ and one structure of CH5
– are calculated using a gaussian basis both in the SCF approximation and with the inclusion of electron correlation in the independent electron pair approximation (IEPA). While on SCF level the C
sstructure of CH5
+ has to lowest energy, the energy difference between the C
sand C
2vstructures becomes negligible if correlation is included. In contrast to this the approach of a proton to CH4 at large and intermediate distances is most favorable towards a corner of the CH4 tetrahedron which means a structure. The decomposition of CH5
+ into CH3
+ and H2 requires 20kcal/mol on SCF level and 40 kcal/mol if correlation is included. 相似文献