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781.
Docoslis A Espinoza LA Zhang B Cheng LL Israel BA Alexandridis P Abbott NL 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):3840-3848
Nonuniform ac (alternating current) electric fields created by microelectrodes are investigated for their influence on the transport of the vesicular stomatitis virus (VSV) from aqueous suspensions of physiological ionic strength to surfaces on which the VSV is captured. Whereas passive diffusion did not lead to detectable levels of virus captured on a surface when using titers of VSV as high as 107 PFU/mL, nonuniform electric field-mediated transport led to the detection of 105 PFU/mL of virus in 2 min. An order-of-magnitude analysis of the time scales associated with virus transport to the microelectrodes inside media of physiological relevance indicates that electrothermal fluid flow (and the resulting viscous drag forces on the virus) rather than dielectrophoresis likely constitutes the major mechanism for virus transport far from the electrodes. The influence of dielectrophoresis was calculated to be confined to a region within a few micrometers of the electrodes and to lead to collection patterns of both virus and fluorescently labeled particles near the electrodes that were found to be in qualitative agreement with experiments. These observations and conclusions are discussed within a theoretical framework presented in the paper. The results presented in this work, when combined, suggest that ac electrokinetic phenomena can be used to expeditiously transport and capture viruses onto surfaces from solutions of high ionic strength, thus providing a potentially useful approach to addressing a bottleneck in the development of devices that allow for rapid sampling and detection of infectious biological agents. 相似文献
782.
783.
784.
The interaction between high-spin Fe7 clusters and a benzene molecule was studied using the BPW91/6-311++G(2d,2p) method. The Fe7-C6H6 ground state has a T-shaped structure, similar to that of the benzene dimer, and a multiplicity M = 2S + 1 = 19 (S = total spin). The carbon atoms are bonded to a single equatorial iron atom, which experiences a dramatic decrease in its magnetic moment, from 3.1 to -0.8 mu(B); the magnetic moments of other Fe atoms are larger than those in the ground-state Fe7 cluster. Such unexpected magnetic behavior of the cluster is crucial for adsorption of benzene. 相似文献
785.
Sankar Muniappan Sophia Lipstman Israel Goldberg 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(3):o177-o179
The title compound, C64H66B4N4O8·2C6H5NO2, is a nitrobenzene solvate of a meso‐tetraphenylporphyrin species with unconventional peripheral boronic ester substituents. The porphyrin units reside in the crystal on centers of inversion and exhibit a channel clathrate‐type structure, wherein molecules of nitrobenzene are accommodated in tunnels of width 7–8 Å that propagate through the crystal parallel to the b axis between layers of tightly offset‐stacked porphyrins. The scientific significance of the reported results is twofold. They describe the synthetic route to newly functionalized building blocks for the formulation of porphyrin‐based supramolecular assemblies, namely the corresponding tetraboronic acid derivative; the title compound represents an essential intermediate in this process. They reveal also that channel‐type clathrates can be formed not only with the parent tetraphenylporphyrins but also with their laterally extended derivatives. 相似文献
786.
787.
A comprehensive study is reported of Langmuir-Blodgett (LB) films (spread at the air/water interface using the Langmuir balance technique) composed of surface active, nonionic, and OH-free amphiphilic siloxane phosphonate ester macromolecules. Analysis is made on three molecular structures in the form of linear polymer poly(diethylphosphono-benzyl-alphabeta-ethyl methylsiloxane) (PPEMS), cyclic oligomer methylphosphonobenzyl-alphabeta-ethyl cyclosiloxane (MPECS), and copolymer poly(PEMS-co-DMS). The surface pressure-surface area (pi -A) isotherms of homopolymer at 3-40 degrees C show a clear temperature-induced phase transition (plateaus at pit approximately 17-19 mN/m) below 10 degrees C. The magnitude of the transition substantially increases upon lowering the temperature (partial differential DeltaAt/ partial differential T approximately -0.1 nm2 unit(-1) deg(-1) and partial differential pi t / partial differential T approximately -0.25 mN m(-1) deg(-1)). The positive entropy and enthalpy gain infers that strong coupling with the subphase and excess hydration attributed to hydrogen bonding between the P=O bond and the subphase prevails at low temperatures. The cyclic oligomer MPECS forms a condensed monolayer at the air/water interface that does not display a similar transition in the experimental temperature range. The temperature sensitivity of MPECS film is observed only in the collapsed region. The nature of the interaction with the subphase is similar for MPECS and PPEMS, indicating that the size and thermal mobility are the controlling factors in these processes. The elasticity plot reveals two distinct states (above and below transition). This observation is supported by BAM images that show irregular spiral structures below 10 degrees C. The transition occurring in the copolymer at 20 degrees C is due to relaxation of the PDMS component. The two maxima shown in the elasticity plot indicate additive fractions of PPEMS and PDMS. The surface areas of these macromolecules in the relaxed (1.48 nm2/unit) and packed (0.45 nm2/unit) forms obtained by PM3 modeling agree well with the experimental data and seem to indicate that the siloxane chain is being lifted off the subphase by the hydrophobic phenylic part of the molecule. 相似文献
788.
Serrano-Pérez JJ González-Ramírez I Coto PB Merchán M Serrano-Andrés L 《The journal of physical chemistry. B》2008,112(45):14096-14098
The higher formation yields measured in the ultrafast photoinduced formation of cyclobutane thymine dimers (T<>T) with respect to those of cytosine (C<>C) are explained, on the basis of ab initio CASPT2 results, by the existence in thymine of more reactive orientations and a less efficient photoreversibility, whereas in cytosine the funnel toward the photolesion becomes competitive with that mediating the internal conversion of the excited-cytosine monomer. 相似文献
789.
Mixed valence (MV) coordination compounds play important roles in redox reactions in chemistry and biology. Details of the contribution of a mixed valence state to protein electron transfer (ET) reactivity such as reorganization energy, however, have not been experimentally defined. Herein we report measurements of reorganization energies of a binuclear CuA center engineered into Pseudomonas aeruginosa azurin that exhibits a reversible transition between a totally delocalized MV state at pH 8.0 and a trapped valence (TV) state at pH 4.0. The reorganization energy of a His120Ala variant of CuA azurin that displays a TV state at both the above pH values has also been determined. We found that the MV-to-TV state transition increases the reorganization energy by 0.18 eV, providing evidence that the MV state of the CuA center has lower reorganization energy than its TV counterpart. We have also shown that lowering the pH from 8.0 to 4.0 results in a similar (approximately 0.4 eV) decrease in reorganization energy for both blue (type 1) and purple (CuA) azurins, even though the reorganization energies of the two different copper centers are different at a given pH. These results suggest that the MV state plays only a secondary role in modulation of the ET reactivity via the reorganization energy, as compared to that of the driving force. 相似文献
790.