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971.
Density functional theory calculations on [LnCp2APh] (Ln = La, Lu; Cp = eta 5-C5H5; A = O, S; Ph = C6H5) suggest that the linearity of the Ln-O-C vectors arises largely as a result of electrostatic repulsion between the alpha carbon and the trivalent metal centre. 相似文献
972.
Alfredsson M Catlow CR Paulidou A Nix RM 《Chemical communications (Cambridge, England)》2002,(18):2128-2129
By performing first-principles Molecular Dynamics simulations at 300 K, we show that water dissociates on the A-La2O3(001) surface giving rise to one exclusive type of hydroxyl-group, which is associated with a surface reconstruction, incorporating an additional oxygen ion into the oxide subsurface, yielding a surface structure that is oxygen rich. 相似文献
973.
974.
975.
Sastre G Vidal-Moya JA Blasco T Rius J Jordá JL Navarro MT Rey F Corma A 《Angewandte Chemie (International ed. in English)》2002,41(24):4722-4726
976.
Koziołkiewicz M Owczarek A Wójcik M Domański K Guga P Stec WJ 《Journal of the American Chemical Society》2002,124(17):4623-4627
A new method of analysis has allowed the exonucleolytic cleavage by human 3'-exonuclease to be determined. Hydrolysis by human plasma 3'-exonuclease proceeds with retention of configuration at phosphorus. The new method determines the sense of chirality at phosphorus in isotopomeric adenosine 5'-O-[(18)O]phosphorothioates. This is based on stereospecific two-step conversion of the mono-thionucleotide into the corresponding deoxyadenosine 5'-O-alpha-[(18)O]thiotriphosphate, followed by the use of terminal deoxyribonucleotidyl transferase and MALDI TOF mass spectrometry of the resulting elongated primer. Retention of configuration in the reaction of plasma 3'-exonuclease implies a two-step mechanism with two displacements on phosphorus. Inversion at each step leads to overall retention. 相似文献
977.
Ballardini R Balzani V Clemente-León M Credi A Gandolfi MT Ishow E Perkins J Stoddart JF Tseng HR Wenger S 《Journal of the American Chemical Society》2002,124(43):12786-12795
We have designed, synthesized, and investigated a self-assembling supramolecular system which mimics, at a molecular level, the function performed by a macroscopic electrical extension cable. The system is made up of three components, 12+, 2-H3+, and 3. Component 12+ consists of two moieties: a [Ru(bpy)3]2+ unit, which plays the role of an electron donor under light excitation, and a DB24C8 crown ether, which fulfills the function of a socket. The wire-type component 2-H3+ is also composed of two moieties, a secondary dialkylammonium-ion center and a bipyridinium unit, which thread into the DB24C8 crown-ether socket of 12+ and the 1/5DN38C10 crown-ether socket 3, respectively. The photochemical, photophysical, and electrochemical properties of the three separated components, of the 12+ superset 2-H3+ and 2-H3+ subset 3 dyads, and of the 12+ superset 2-H3+ subset 3 triad have been investigated in CH2Cl2 solution containing 2% MeCN. Reversible connection/disconnection of the two plug/socket systems can be controlled independently by acid/base and redox stimulation. The behavior of the various different dyads and triad has been monitored by light absorption and emission spectroscopies, as well as by electrochemical techniques. In the fully connected 12+ superset 2-H3+ subset 3 triad, light excitation of the [Ru(bpy)3]2+ unit of component 12+ is followed by electron transfer (k = 2.8 x 108 s-1) to the bipyridinium unit of component 2-H3+, which is plugged into component 3. Possible schemes to obtain improved molecular-level electrical extension cables are discussed. 相似文献
978.
Kowalewski J Effemey M Jokisaari J 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2002,157(2):171-177
Multiple-field (4.7, 9.4, 14.1 T) carbon-13 relaxation data are reported for hexamethylenetetramine (HMTA) in the cryosolvent D(2)O/DMSO at 243 K. Under these conditions, the reorientational motion of HMTA is outside of the extreme narrowing range and the relaxation data can be subjected to a quantitative interpretation. Because of the high symmetry of the HMTA molecule, the reorientation must be isotropic. Treating the reorientation as a small-step rotational diffusion of a rigid body, we obtain a rotational correlation time of 1.0 ns and a carbon-proton dipole-dipole coupling constant corresponding to an effective internuclear distance of 114. 2 pm. The harmonic vibrational correction to the dipole-dipole coupling constant, based on a known force field, yields an NMR estimate of the r(alpha) distance of 110.8 +/- 0.3 pm. 相似文献
979.
In the paper calculation of the moments of inertia for nuclei from the region 87 ≤ Z ≤ 100 and 130 ≤ N ≤ 156 was made in dependence on the angular momentum of their rotational states. The experimental values of the moments of
inertia were calculated for rotational energy of the classic rotor in its quantum form, with the use of a simple formula.
The moment of inertia term appearing in the formula was treated as a variable. The calculations were carried out on the basis
of experimental data for the energies of the rotational levels for 51 bands built on ground states for even-even nuclei and
for nuclei with odd mass number A. In addition, 30 rotational bands built on excited states were also analysed in the investigated region in case of even-even
nuclei. For many bands and nuclei the considered dependence of the moment of inertia on angular momentum has been found in
the analytical form by fitting polynomials to the experimental data. It turned out that obtained results for the moments of
inertia made it possible to describe the energies of rotational levels with a relative deviation not greater or only slightly
greater than 1%. In general, in the case of 12 bands of ground level the maximum relative deviation of obtained level energies
is smaller than 1%.
相似文献
980.
Marina Quartu Maria Pina Serra Marianna Boi Viviana Ibba Tiziana Melis Marina Del Fiacco 《BMC neuroscience》2008,9(1):108