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121.
The theoretical electrophilicity pattern of a series of benzhydryl cations as described in terms of a model based on global reactivity indexes is compared with an experimental scale recently proposed by Mayr et al. [J. Am. Chem. Soc. 2001, 123, 9500]. A good correlation between both theoretical and experimental quantities is found. The effect of chemical substitution on the electrophilic power of these charged electrophiles may also be assessed as local responses at the active site, in terms of a global contribution described by changes in global electrophilicity with reference to the dianisylcarbenium ion, and a local contribution described by the variations in electrophilic Fukui function at that site.  相似文献   
122.
The bulk mixed Mo-V-Te oxides possess high activity and selectivity in propane oxidation to acrylic acid and represent well-defined model catalysts for studies of the surface molecular structure-activity/selectivity relationships in this selective oxidation reaction. The elemental compositions, metal oxidation states, and catalytic functions of V, Mo, and Te in the surface region of the model Mo-V-Te-O system were examined employing low energy ion scattering (LEIS) and X-ray photoelectron spectroscopy (XPS). This study indicated that the surfaces of these catalysts are terminated with a monolayer, which possesses a different elemental composition from that of the bulk. The rates of propane consumption and formation of propylene and acrylic acid depended on the topmost surface V concentration, whereas no dependence of these reaction rates on either the surface Mo or Te concentrations was observed. These findings suggested that the bulk Mo-V-Te-O structure may function as a support for the unique active and selective surface monolayer in propane oxidation to acrylic acid. The results of this study have important practical consequences for the development of improved selective oxidation catalysts by introducing surface metal oxide components to form new surface active V-O-M sites for propane oxidation to acrylic acid.  相似文献   
123.
The electromagnetic and geometric characteristics of electron beams generated by molybdenum cathodes illuminated by an excimer laser are reported. To determine the electromagnetic characteristics, a fast Rogowski coil was utilized, while the geometric characteristics were performed by a suitable slit–slit meter system. During the experiment the laser spot on the cathode was fixed to 4 mm2. The maximum output current (370 mA) was reached with 0.5 mJ laser energy and 50 kV accelerating voltage. In these conditions the electron beam normalized emittance was 6 (π mm mrad) calculated at 80% level current density. The laser used in this experiment was a singular excimer laser (KrCl) operating in the NUV range. Received: 22 March 2000 / Revised version: 11 July 2000 / Published online: 5 October 2000  相似文献   
124.
 Forensic examination results play an increasingly important role in bringing many criminal investigations to a successful conclusion. The quality of the results of examinations performed in forensic science laboratories has always been the concern of the individual forensic scientist. The interpretations and results are presented in court to non-experts. Therefore, it is essential to ensure and maintain the highest standards of achievements and accuracy in forensic science. Many factors are important contributors to quality assurance in forensic science. Some unique subjects affect not only the mode of inquiry but also the way in which information is presented to the court, i.e. exhibits collection and sample handling, investigation, examination techniques, report writing and court testimony.  相似文献   
125.
The motional properties of rhodamine green alone and conjugated to 10-kDa dextran have been studied by fluorescence correlation spectroscopy (FCS) and time-resolved fluorescence anisotropy (TRFA). With FCS the translational diffusion times of the fluorescent particles can be determined, which are directly proportional to the shear viscosity as shown in aqueous solutions of different sucrose concentrations. With TRFA the rotational correlation times of the fluorescent particles can be determined. TRFA experiments in the case of fluorescent dextran reveal a distinct restricted internal motion of the fluorescent probe independent of the slower overall rotation of the polysaccharide. The fast depolarization is most likely due to internal motion and not to energy transfer between different rhodamine green molecules in the same dextran, since a higher viscosity of the solvent increases the correlation time for internal motion proportionally. FCS and TRFA yield complementary information in the sense that the correlation time for overall dextran rotation can be accurately determined from the translational diffusion coefficient.  相似文献   
126.
We report the synthesis of several new α-trifluoromethylated nitrogen heterocycles, among which azanorbornene and azetidine derivatives, by aza Diels–Alder or iodine-mediated cyclizations. These building blocks were used as starting materials for the formation of fluorinated polymers by ROMP or for ligand design through substitution and click reactions.  相似文献   
127.
Eight banana-shaped side chain liquid crystalline oligomers and polymers have been synthesized by hydrosilylation of vinyl-terminated bent-core mesogens with trimethylsilyl-terminated siloxanes. The synthesized oligomers and polymers, and their olefinic precursors, were investigated by polarizing optical microscopy (POM), differential scanning calorimetry, X-ray diffraction (XRD), electro-optical experiments and Maldi-Tof. The short-tailed olefins form a Colr mesophase, whereas those with longer chains exhibit the SmCPA mesophase. All the oligomers and polymers studied show liquid crystalline properties and do not crystallize upon cooling. Most oligomers with around four repeating siloxane units, show a lamellar (layer) structure and antiferroelectric switching properties, the SmCPA phase. XRD shows that the layer spacings are hardly influenced by the length of the terminal tails. The oligomer prepared from the smallest olefinic precursor, having the shortest alkyl tail, shows an XRD pattern reminiscent of a columnar phase, although POM displays domains of opposite chirality, and no switching behaviour could be detected. The polymers with around 35 repeating siloxane units are liquid crystalline, but due to their high viscosity a thorough characterization of the liquid crystalline phases was impossible.  相似文献   
128.
The paper investigates the asymptotic theory for a multivariate GARCH model in its general vector specification proposed by Bollerslev, Engle and Wooldridge (1988) [4], known as the VEC model. This model includes as important special cases the so-called BEKK model and many versions of factor GARCH models, which are often used in practice. We provide sufficient conditions for strict stationarity and geometric ergodicity. The strong consistency of the quasi-maximum likelihood estimator (QMLE) is proved under mild regularity conditions which allow the process to be integrated. In order to obtain asymptotic normality, the existence of sixth-order moments of the process is assumed.  相似文献   
129.
A moiré interferometer is used to measure the thermal expansion of two ferroelectric crystals, LiNbO3 and KTiOPO4. The crystal samples are patterned with a chromium reflective grating and used as a diffractive component in a reflective grating interferometer. The thermal expansion of all the three axes of congruent LiNbO3 and of x and y axes of the flux-grown KTiOPO4 were measured from room temperature to 200 °C. For this temperature range the thermal expansion coefficient has been modeled by a second-order polynomial and its coefficients have been estimated by accurate analysis of the resulting moiré fringe pattern.  相似文献   
130.
We develop a theory for frictional drag between two 2D hole layers in a dilute bilayer GaAs hole system, including effects of hole-hole and hole-phonon interactions. Our calculations suggest significant enhancement of hole drag transresistivity over the corresponding electron drag results. This enhancement originates from the exchange induced renormalization of the single-layer compressibility and the strong dependence of single-layer conductivity on density. We also address the effect of hole-phonon interaction on the drag temperature dependence. Our calculated results are in reasonable quantitative agreement with recent experimental observations.  相似文献   
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