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861.
We study planar waves in a circulating, draining fluid flow, which: (i) exhibit an analogue of the Aharonov-Bohm (AB) effect in Quantum Mechanics; (ii) obey a Klein-Gordon equation on an ‘effective spacetime’ which resembles the Kerr spacetime of General Relativity; and (iii) may be observed in the laboratory using gravity waves in a shallow basin. We describe a modified AB effect which depends on two dimensionless parameters, associated with the circulation α and draining β rates; we call this the ‘αβ effect’. We show that the αβ effect is inherently asymmetric even in the low-frequency limit, and that it leads to novel interference patterns which carry the signature of both rotation and absorption.  相似文献   
862.
A polymer must reach a certain size to exhibit significant excluded-volume interactions and adopt a swollen random-walk configuration. We show that single-molecule measurements can sense the onset of swelling by modulating the effective chain size with force: as the force is reduced from a large value, the polymer is first highly aligned, then a Gaussian coil, then finally a swollen chain, with each regime exhibiting a distinct elasticity. We use this approach to quantify the structural parameters of poly(ethylene glycol) and show that they vary in the expected manner with changes in solvent.  相似文献   
863.
Han SP  Ko H  Kim N  Ryu HC  Lee CW  Leem YA  Lee D  Jeon MY  Noh SK  Chun HS  Park KH 《Optics letters》2011,36(16):3094-3096
The successful demonstration of an optical fiber-coupled terahertz time-domain spectroscopy (THz-TDS) system is described in this study. The terahertz output power of the emitter with two optical band rejection filters was 132 nW, which is an improvement of 70% over the output power without any filters. This improvement is due to the suppression of an optical modulated signal that is reverse-generated when an alternating current bias exceeding a certain threshold is applied to the emitter. Under the optimal alignment conditions, the terahertz detector in a fiber-coupled THz-TDS system clearly measured water vapor dips in the free space.  相似文献   
864.
The structural and photoluminescence analyses were performed on un-doped and Mn doped ZnO thin films grown on Si (1 0 0) substrate by pulsed laser deposition (PLD) and annealed at different post-deposition temperatures (500-800 °C). X-ray diffraction (XRD), employed to study the structural properties, showed an improved crystallinity at elevated temperatures with a consistent decrease in the lattice parameter ‘c’. The peak broadening in XRD spectra and the presence of Mn 2p3/2 peak at ∼640 eV in X-ray Photoelectron Spectroscopic (XPS) spectra of the doped thin films confirmed the successful incorporation of Mn in ZnO host matrix. Extended near band edge emission (NBE) spectra indicated the reduction in the concentration of the intrinsic surface traps in comparison to the doped ones resulting in improved optical transparency. Reduced deep level emission (DLE) spectra in doped thin films with declined PL ratio validated the quenching of the intrinsic surface traps thereby improving the optical transparency and the band gap, essential for optoelectronic and spintronic applications. Furthermore, the formation and uniform distribution of nano-sized grains with improved surface features of Mn-doped ZnO thin films were observed in Field Emission Scanning Electron Microscopy (FESEM) images.  相似文献   
865.
Iron(IV)–oxo intermediates are involved in oxidations catalyzed by heme and nonheme iron enzymes, including the cytochromes P450. At the distal site of the heme in P450 Compound I (FeIV–oxo bound to porphyrin radical), the oxo group is involved in several hydrogen‐bonding interactions with the protein, but their role in catalysis is currently unknown. In this work, we investigate the effects of hydrogen bonding on the reactivity of high‐valent metal–oxo moiety in a nonheme iron biomimetic model complex with trigonal bipyramidal symmetry that has three hydrogen‐bond donors directed toward a metal(IV)–oxo group. We show these interactions lower the oxidative power of the oxidant in reactions with dehydroanthracene and cyclohexadiene dramatically as they decrease the strength of the O? H bond (BDEOH) in the resulting metal(III)–hydroxo complex. Furthermore, the distal hydrogen‐bonding effects cause stereochemical repulsions with the approaching substrate and force a sideways attack rather than a more favorable attack from the top. The calculations, therefore, give important new insights into distal hydrogen bonding, and show that in biomimetic, and, by extension, enzymatic systems, the hydrogen bond may be important for proton‐relay mechanisms involved in the formation of the metal–oxo intermediates, but the enzyme pays the price for this by reduced hydrogen atom abstraction ability of the intermediate. Indeed, in nonheme iron enzymes, where no proton relay takes place, there generally is no donating hydrogen bond to the iron(IV)–oxo moiety.  相似文献   
866.
Abstract

Studies have been made on the characterizations and conductivities of poly(methyl vinyl ketone) (PMVK) and its copolymer with methyl methacrylate (poly(MVK-co-MMA)) after being reacted with phosphorus oxychloride (POCl3). The POCl3?treated polymers containing methyl vinyl ketone (MVK) were characterized by IR and UV spectroscopies to prove the structure of conjugated double bonds. The conductivities of all the MVK-containing polymers treated with POCl3 were very low, ca. 10?17 S/cm, in a vacuum regardless of the treatment time. The conductivities of the polymers when doped with iodine are in the range of the order of 10?4 to 10?6 S/cm. It was found that the conductivity of the POCl3?treated copolymer is slightly lower than that of PMVK.  相似文献   
867.
This study was carried-out to leach uranium from rock phosphate using sulphuric acid in the presence of potassium chlorate as an oxidant and to investigate the relative purity of different forms of yellow cakes produced with ammonia, magnesia and sodium hydroxide as precipitants, as well as purification of the products with TBP and matching its impurity levels with specifications of the commercial products. Alpha-particle spectrometry was used for determination of activity concentration of uranium isotopes in rock phosphate, resulting phosphoric acid, and in different forms of the yellow cake. Likewise, atomic absorption spectroscopy was used for determination of impurities. On the average, the equivalent mass concentration of uranium was 119.38 ± 79.66 ppm (rock phosphate) and 57.85 ± 20.46 ppm (phosphoric acid) with corresponding low percent of dissolution (48 %) which is considered low. The isotopic ratio (234U:238U) in all stages of hydrometallurgical process was not much different from unity indicating lack of fractionation. Upon comparing the levels of impurities in different form of crude yellow cakes, it was found that the lowest levels were measured in hydrated trioxide (UO3·xH2O). This implies that saturated magnesia is least aggressive relative to other precipitants and gives relatively pure crude cake. Therefore, it was used as an index to judge the relative purity of other forms of yellow cakes by taking the respective elemental ratios. The levels of impurities (Fe, Zn, Mn, Cu, Ni, Cd and Pb) in the purified yellow cake were found comparable with those specified for commercial products.  相似文献   
868.
AlkB repair enzymes are important nonheme iron enzymes that catalyse the demethylation of alkylated DNA bases in humans, which is a vital reaction in the body that heals externally damaged DNA bases. Its mechanism is currently controversial and in order to resolve the catalytic mechanism of these enzymes, a quantum mechanics/molecular mechanics (QM/MM) study was performed on the demethylation of the N1‐methyladenine fragment by AlkB repair enzymes. Firstly, the initial modelling identified the oxygen binding site of the enzyme. Secondly, the oxygen activation mechanism was investigated and a novel pathway was found, whereby the catalytically active iron(IV)–oxo intermediate in the catalytic cycle undergoes an initial isomerisation assisted by an Arg residue in the substrate binding pocket, which then brings the oxo group in close contact with the methyl group of the alkylated DNA base. This enables a subsequent rate‐determining hydrogen‐atom abstraction on competitive σ‐ and π‐pathways on a quintet spin‐state surface. These findings give evidence of different locations of the oxygen and substrate binding channels in the enzyme and the origin of the separation of the oxygen‐bound intermediates in the catalytic cycle from substrate. Our studies are compared with small model complexes and the effect of protein and environment on the kinetics and mechanism is explained.  相似文献   
869.
Blending different low molecular weight gelators (LMWGs) provides a convenient route to tune the properties of a gel and incorporate functionalities such as fluorescence. Blending a series of gelators having a common bis‐urea motif, and functionalised with different amino acid‐derived end‐groups and differing length alkylene spacers is reported. Fluorescent gelators incorporating 1‐ and 2‐pyrenyl moieties provide a probe of the mixed systems alongside structural and morphological data from powder diffraction and electron microscopy. Characterisation of the individual gelators reveals that although the expected α‐urea tape motif is preserved, there is considerable variation in the gelation properties, molecular packing, fibre morphology and rheological behaviour. Mixing of the gelators revealed examples in which: 1) the gels formed separate, orthogonal networks maintaining their own packing and morphology, 2) the gels blended together into a single network, either adopting the packing and morphology of one gelator, or 3) a new structure not seen for either of the gelators individually was created. The strong binding of the urea functionalities to anions was exploited as a means of breaking down the gel structure, and the use of fluorescent gel blends provides new insights into anion‐mediated gel dissolution.  相似文献   
870.
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