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1.
Mono‐ and octa‐azobenzene‐functionalized cage silsesquioxanes were easily synthesized by the reaction of 4‐bromoazobenzene with monovinyl‐substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited‐state energies obtained from time‐dependent density functional theory (TDDFT) and the CAM‐B3LYP functional correlate very well with experimental trans–cis photoisomerization results from UV/Vis spectroscopy. These azobenzene‐functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue‐light emission.  相似文献   
2.
In the past, the preferred strategy for the identification of unknown compounds was to search in an appropriate mass spectral database for spectra obtained using either electron ionisation (GC‐MS analyses) or collision‐induced dissociation (LC‐MS/MS analyses). Recently, an increase has been seen in the use of accurate mass instruments and spectra‐less databases, based on monoisotopic accurate mass alone. In this article, we describe a systematic workflow for the screening and identification of new flame retardants. This approach utilises LC‐quadrupole‐time‐of‐flight MS and spectra‐less databases based only on monoisotopic accurate mass for the identification of ‘unknowns’. An in‐house database was built, and the input parameters used in the data analysis process were optimised for flame retardant chemicals, so that it can be easily transferred to other laboratories. The procedure was successfully applied to dust, foam and textiles from car interiors and indoor consumer products. The developed method was demonstrated for the main new flame retardant present in Antiblaze V6 and for the three unreported reaction by‐products/impurities present in the same technical mixture. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   
3.
We report both the experimental and theoretical insights of differential electro‐diffusion behavior of carbon nanomaterials (e.g. single wall, multiwall carbon nanotubes, and graphene). We thus discriminate one from the other in a soft gel system. The differential mobility of such material depends on their intrinsic properties, both extend and rate of migration bearing the discriminatory signature. The mobility analysis is made by a real time monitoring of the respective bands.  相似文献   
4.
We consider a compound Poisson risk model with interest. The Gerber–Shiu discounted penalty function is modified with an additional penalty for reaching a level above the initial capital. We show that the problem can be split into two independent problems; an original Gerber–Shiu function and a first passage problem. We also consider the case of negative interest. Finally, we apply the results to a model considered by Embrechts and Schmidli (1994).  相似文献   
5.
In this paper we generalize a partial integrodifferential equation satisfied by the finite time ruin probability in the classical Poisson risk model. The generalization also includes the bivariate distribution function of the time of and the deficit at ruin. We solve the partial integrodifferential equation by Laplace transforms with the help of Lagrange’s implicit function theorem. The assumption of mixed Erlang claim sizes is then shown to result in tractable computational formulas for the finite time ruin probability as well as the bivariate distribution function of the time of and the deficit at ruin. A more general partial integrodifferential equation is then briefly considered.  相似文献   
6.
In this paper we consider two linear differential systems on a time scale. Both systems depend linearly on a complex spectral parameter λ. We prove that if all solutions of these two systems are square integrable with respect to a given weight matrix for one value λ0, then this property is preserved for all complex values λ. This result extends and improves the corresponding continuous time statement, which was derived by Walker (1975) for two non‐hermitian linear Hamiltonian systems, to appropriate differential systems on arbitrary time scales. The result is new even in the purely discrete case, or in the scalar time scale case, as well as when both time scale systems coincide. The latter case also generalizes a limit circle invariance criterion for symplectic systems on time scales, which was recently derived by the authors.  相似文献   
7.
8.
Recent experimental observations of enhanced vibrational circular dichroism (VCD) in molecular systems with low‐lying electronically excited states suggest interesting new applications of VCD spectroscopy. The theory describing VCD enhancement through vibronic coupling schemes was derived by Nafie in 1983, but only recently experimental evidence of VCD amplification has demonstrated the extent to which this effect can be exploited as a structure elucidation tool to probe local structure. In this Concept paper, we give an overview of the physics behind vibrational circular dichroism, in particular the equations governing the VCD amplification effect, and review the latest experimental developments with a prospective view on the application of amplified VCD to locally probe biomolecular structure.  相似文献   
9.
As is well‐known, the C2?H proton of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ([Emim]BF4) and 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([Bmim]BF4) has a strong ability to form hydrogen bonds. The purpose of this work is to evaluate the effect of the interactions of the C4?H and C5?H protons on the microstructure of [Emim]BF4 and [Bmim]BF4 with water by using 1H NMR spectroscopy. The differences between the relative 1H NMR chemical shifts of C2?H, C4?H, and C5?H and between the interaction‐energy parameters obtained from these chemical shifts are minor, thus suggesting that the interactions of C4?H and C5?H may have a considerable effect on the microstructure. To confirm this, the viscosities of the systems are estimated by using the interaction‐energy parameters obtained from the 1H NMR chemical shifts of the three studied aromatic protons and water, showing that the interactions of C4?H and C5?H also play an important role in the microstructure.  相似文献   
10.
An ultra‐performance liquid chromatography coupled with quadrupole time‐of‐flight mass spectrometry method integrating multi‐constituent determination and fingerprint analysis has been established for quality assessment and control of Scutellaria indica L. The optimized method possesses the advantages of speediness, efficiency, and allows multi‐constituents determination and fingerprint analysis in one chromatographic run within 11 min. 36 compounds were detected, and 23 of them were unequivocally identified or tentatively assigned. The established fingerprint method was applied to the analysis of ten S. indica samples from different geographic locations. The quality assessment was achieved by using principal component analysis. The proposed method is useful and reliable for the characterization of multi‐constituents in a complex chemical system and the overall quality assessment of S. indica.  相似文献   
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