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101.
Intramolecular vibrational energy redistributions of the O-H stretching (nuOH) vibration for the methanol monomer and its water complex, the methanol-water dimer, are investigated by using ab initio full-dimensional classical trajectory calculations. For the methanol monomer, in the high-energy regime of the 5nuOH overtone, the time dependence of the normal-mode energies indicates that energy flowed from the initial excited O-H stretching mode to the C-H stretching mode. This result confirms the experimental observation of energy redistribution between the O-H and C-H stretching vibrations [L. Lubich et al., Faraday Discuss. 102, 167 (1995)]. Furthermore, a lot of dynamical information in the time domain is contained in the power spectra, whose density is given by the Fourier transformation of the total momentum obtained from trajectory calculations. For the methanol-water hydrogen-bonded complex, at the high-energy level of the 5nuOH overtone, the calculated power spectrum shows considerable splitting and broadening, indicating significant energy redistribution through strong coupling between the O-H stretching vibration and other vibrations. It is thus clear that the A-H...B hydrogen-bond formation facilitates energy redistribution subsequent to the vibrational excitation of the hydrogen-bonded A-H stretching mode.  相似文献   
102.
Thermolysis of 2,5-diphenyl-1,4-dithiin-1-oxide afforded 2-formyl-2,4-diphenyl-1,3-dithiole, which was obtained also in photolysis along with another rearranged product, 2-benzoyl-4-phenyl-1,3-dithiole.  相似文献   
103.
The cyclization of 2-(1-alkynyl)-2-alken-1-ones 1 proceeded very smoothly in the presence of alcohols 2 with a catalytic amount of Cu(I)Br in DMF at 80 degrees C, leading to the formation of highly substituted furans 3. The catalytic system reported herein is easy to handle, compared to the previously known system wherein the reaction between 1 and 2 needed to use moisture sensitive gold(III) chloride.  相似文献   
104.
Mao L  Shi G  Tian Y  Liu H  Jin L  Yamamoto K  Tao S  Jin J 《Talanta》1998,46(6):1547-1556
A novel thin-layer amperometric detector (TLAD) based on chemically modified ring-disc electrode and its application for simultaneous measurements of nitric oxide (NO) and nitrite (NO2) in rat brain were demonstrated in this work. The ring-disc electrode was simultaneously sensitive to nitric oxide (NO) and nitrite (NO2) by modifying its inner disc with electropolymerized film of cobalt(II) tetraaminophthalocyanine (polyCoTAPc)/Nafion and its outer ring with poly(vinylpyridine) (PVP), respectively. The ring-disc electrode was used to constitute a novel TLAD in radial flow cell for simultaneous measurements of NO and NO2 in rat brain combined with techniques of high performance liquid chromatography (HPLC) and in vivo microdialysis. It was found that the basal concentration of NO in the caudate nucleus of rat brain is lower than 1.0×10−7 mol l−1, NO2 concentration is 5.0×10−7 mol l−1 and NO exists in brain maybe mainly in the form of its decomposed product.  相似文献   
105.
106.
A microanalytical method for the determination of traces of natural brassinosteroids as their dansylaminophenylboronates by liquid chromatography with fluorimetric detection is described. The boronates are easily prepared by the reaction of brassinosteroids with dansylaminophenylboronic acid (DABA), which was newly synthesized as a precolumn fluorogenic reagent for brassinosteroids. The potential of the method is demonstrated by the separation of a standard brassinosteroid mixture and the analysis of a biologically active fraction sample obtained from an extract of Zea mays L. pollen. The detection limit of the DABA derivative was found to be 25 pg for brassinolide, which is superior to that of the phenanthreneboronate derivative.  相似文献   
107.
The synthetic route for a uterine relaxant, bis(2-[[(2S)-2-([(2R)-2-hydroxy-2-[4-hydroxy-3-(2-hydroxyethyl)-phenyl]ethyl]amino)-1,2,3,4-tetrahydronaphthalen-7-yl]oxy]-N,N-dimethylacetamide) sulfate (KUR-1246), was established by the coupling of optically active components, the bromohydrin 14 and the amine 24. We now describe the practical synthesis of these two optically active components. Bromohydrin 14 was obtained by the asymmetric borane reduction of the prochiral phenacyl bromide 13 using a catalyst prepared from aluminum triethoxide and a chiral amino alcohol. The other optically active component 24 was prepared from (S)-AMT.  相似文献   
108.
Silicone has been utilized as a carrier material for sustained release system of lipophilic drugs. Extensive studies revealed that drug release rate is influenced by factors such as physicochemical properties of the drug and additives.(1-5)) When a lipophilic drug is highly potent at low concentrations, the drug release rate should be strictly controlled so as to avoid side effects. In this study, using vitamin D(3) (VD(3)) as an example of such drugs, we investigated novel method to suppress initial burst and to modify drug release rate from silicone matrix. As a result, it was found that (a). addition of human serum albumin (HSA) suppressed initial burst and enhanced release rate in the later stage, resulting constant release of VD(3), (b). covering a matrix formulation with a membrane of low diffusivity (core-rod formulation) suppressed initial burst and released drug in a constant rate, and (3) using materials for which the drug has high affinity as dissolution solvent (reservoir formulation), the drug release rate was reduced.  相似文献   
109.
Growth of colloidal particles formed during the sol-gel transition of a resorcinol-formaldehyde (RF) solution was simulated based on the population balance equation by using the discrete-sectional model (DSM). During the early stage of the sol-gel transition, the transient change of sizes of colloidal particles estimated by this method agreed well with the previous experimental observation by dynamic light scattering (DLS), which confirmed the influence of the catalyst concentration of a starting RF solution on the growth rate of the particles. From the size distribution of colloidal particles predicted at the gelation time, the surface area of a RF hydrogel after the completion of the sol-gel transition was estimated, which coincided with the BET surface area of a RF aerogel because the porous structure of a hydrogel was maintained and few micropores were formed during supercritical drying.  相似文献   
110.
A negative-ion-based neutral beam injector (N-NBI) has been constructed for JT-60U. The N-NBI is designed to inject 500 keV, 10 MW neutral beams using two ion sources, each producing a 500 keV, 22 A D ion beam. In the preliminary experiment using one ion source, a D ion beam of 13.5 A has been successfully accelerated with an energy of 400 keV (5.4 MW) for 0.12 s at an operating pressure of 0.22 Pa. This is the highest D beam current and power in the world. Co-extracted electron current was effectively suppressed to the ratio of Ie/ID < 1. The highest energy beam of 460 keV, 2.4 A, 0.44 s has also been obtained. To realize 1 MeV class NBI system for ITER (International Thermonuclear Experimental Reactor), demonstration of ampere class negative ion beam acceleration up to 1 MeV is an important mile stone. To achieve the mile stone, a prototype accelerator and a 1 MV, 1 A test facility called MeV Test Facility (MTF) were constructed. Up to now, an H ion beam was accelerated up to the energy of 805 keV with an acceleration drain current of 150 mA for 1 s in a five stage electrostatic multi-aperture accelerator.  相似文献   
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