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581.
582.
The thermo-optical properties of various types of textures (the homeotropic, planar, and tilted aligned and non-aligned textures) in liquid crystalline materials with smectic A mesophase have been investigated. Investigations have been carried out for large temperature interval and at the direct smectic A mesophase–isotropic liquid (SmA–I) and isotropic liquid–smectic A mesophase (I–SmA) phase transitions that have been carried out. Homogeneous mixtures of 4-n-octyl-4′-cyanobiphenyl with 4-n-decyl-4′-cyanobiphenyl were the objects of the investigations. Temperature dependences of the optical transmission for aligned and non-aligned textures have been measured. Temperature widths of the heterophase regions for the SmA–I and I–SmA phase transitions have been determined. The temperature shift in the optical transmission dependences to low temperatures for the reverse I–SmA phase transition temperatures and the thermal hysteresis has been found for the aligned and non-aligned textures.  相似文献   
583.
Journal of Thermal Analysis and Calorimetry - Fluorescein dye was prepared and characterized on the basis of microanalytical methods, FTIR, NMR and UV–visible spectroscopy in order to ensure...  相似文献   
584.
The bromination reaction of p-benzoquinone-fused norbornadiene was studied at various temperatures (?78, ?50, 0, 25, and 77 °C). At room temperature, the double bonds of the p-benzoquinone units were mainly brominated. The double bond of the norbornene unit also underwent a bromination reaction in a yield of only 2%. However, the reaction at ?78 °C resulted in the formation of products derived from the attack of bromine on the norbornene double bond with higher charge density. In contrast to the bromination reaction, the epoxidation reaction of the same compound with m-chloroperbenzoic acid and dimethyldioxirane exclusively resulted in the formation of products derived from the addition to the double bond of norbornadiene. The regioselectivity observed was investigated and the results were supported by theoretical calculations.  相似文献   
585.
    
Dynamics of changes of the morphological properties and processes of orientation in lyotropic nematic mesophases by application of external magnetic field have been investigated in detail. The dynamics of changes of the optical birefringence values in nematic‐calamitic mesophase vs. time has been determined. The optical mappings of nonequilibrium magnetically induced textures, which have been observed for this mesophase during orientational process, and changes of birefringence vs. time are presented. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   
586.
    
This paper presents a new heterogeneous multiscale modeling method for porous media flows. Physics at the global level is governed by one set of PDEs, while features in the solution that are beyond the resolution capacity of the global model are accounted for by the next refined set of governing equations. In this method, the global or coarse model is given by the Darcy equation, while the local or refined model is given by the Darcy–Stokes equation. Concurrent domain decomposition where global and local models are applied to adjacent subdomains, as well as overlapping domain decomposition where global and local models coexist on overlapping domains, is considered. An interface operator is developed for the case where global and local models commute along the common interface. For the overlapping decomposition, a residual‐based coupling technique is developed that consistently facilitates bottom‐up embedding of scale effects from the local Darcy–Stokes model into the global Darcy model. Numerical results are presented for nonoverlapping and overlapping domain decompositions for various benchmark problems. Computed results show that the hierarchically coupled models accurately account for the heterogeneity of the medium and efficiently incorporate local features into the global response. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   
587.
    
Structures and properties were obtained by density functional calculations for the complexes [RhCl(CO)2(L)] (L = isoquinoline ligands) containing close Rh····H separations. Electrostatic repulsion keeps the atoms apart and Rh····C separations are prevented from developing much further by ligand inflexibility. Natural bond orbital analysis shows small components of C–Hσ to Rh (agostic) donation and Rh to C–Hσ* backdonation. Both σ- and π-electron-withdrawing substituents produce an increase in the Rh····H separation, while ligand inflexibility prevents σ- and π-electron-donating substituents from decreasing the Rh····C separation. Substitution at C2 by Me closes up the Rh····H separation and CHMe2 and CMe3 groups cause a structural change which minimises the interaction. Substitution at C2 by a Ph group gives the shortest Rh····H separation (2.187 Å) and largest Rh to C–Hσ* backdonation. Electron donation at C7 or at C7 and C9 increases the Rh····H separation, as the ligand flexes substantially to accommodate a decrease in the Rh····C separation. On the basis of the minimal C–Hσ to Rh (agostic) donation involved, the complexes are best described as preagostic.  相似文献   
588.
    
A comparative study using NMR spectroscopy and designed top‐pan molecular balances demonstrates that the noncovalent interaction of a hydroxy group with π‐deficient pyrazine and quinoxaline units involves a lone pair–heteroarene interaction which is much stronger and solvent independent when measured relative to the classical π‐facial hydrogen bond to a benzene ring. Alkyl fluorides also prefer the heteroarene rings over the benzene ring. The attractive interaction between a quinoxaline and a terminal alkyne is also stronger than the intramolecular hydrogen bond to an arene.  相似文献   
589.
    
Radiotracer batch ion‐exchange experiments were employed to investigate the uptake of 90Sr and 137Cs radioisotopes by various cation‐exchanged forms of a 30% cross‐linked macroporous 1‐vinyl‐2‐pyrrolidone–divinylbenzene cation‐exchange resin with 1.37 ml g?1 pore volume, 0.0232 µm pore diameter and 271.2 m2 g?1 surface area. The uptake of 90Sr and 137Cs was determined by taking liquid aliquots at various time intervals from solutions over solids. The volume‐to‐solid ratio was kept at 200. The results of kinetic experiments for the carrier‐free 90Sr and 137Cs were evident in all cationic forms of the resin. The percentage uptake and distribution coefficient Kd values with carrier (0.005 M SrCl2 and 0.01 M CsCl) concentrations were also determined, and the best results were obtained from the Li+ and H+ forms of the resin. Cerenkov counting (β?‐counting) was used to observe the initial and final radioactivity in the liquid phase. All the experiments were carried out at room temperature and the radioactivity in each case was corrected for the background counts. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   
590.
We report that an equilibrium mixture of triangular and square supramolecular species results when the flexible, ditopic donor unit, trans-bis(4-pyridyl)ethylene, is reacted with the ditopic acceptor unit, cis-(Me(3)P)(2)Pt(OTf)(2), in a one-to-one ratio. Both products are characterized in solution, by way of multinuclear NMR, and in the solid state, via X-ray crystallography. The effects of water and anions, cobalticarborane versus triflate, on the equilibrium are probed. The selective crystallization of either of the two species can be accomplished via the appropriate choice of solvents and ratio of anions present in the system. The dominant species in solution is not always consistent with the most prevalent species in the solid state.  相似文献   
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