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31.
The molecular geometry of perfluoro(methyloxirane) has been studied using gas-phase electron diffraction data, effective least-squares refinement of the structure being achieved with the aid of constraints to limit the number of variable parameters. With the CCF3 bond constrained to be 0.078 Å longer than the ring CC, the refined bond- length values CF (av.) = 1.323(2), CO (av.) = 1.410(8), and CC (ring) = 1.467(7) Å (rg values, with e.s.d. in parentheses) were obtained; the angles between ring bonds and substituent CF bonds were CCF (av.) 121(1) and OCF (av.) 114(1)o, the corresponding parameters involving the bulkier CCF3 fragment being larger by 3o in each case [∠CCCF3 124(1)o∠OCCF3 117(2)o]. The remaining refined parameters were ∠CCF(of CF3) = 110.6(4)o and τ , a torsion angle defining the orientation of the CF bonds of the CF3 group with respect to ring bonds, = 29(2)o. Dependent bond angles possessed the values 62.7 (COC), 58.7 [OCC (ring)], 108.3 [FCF (CF3 group)], 114 [FCF (ring CF2)], and 111o (FCCF3).  相似文献   
32.
Substituted pyridones and pyridines have been synthesised efficiently by employing iminium salt as a key precursor. These compounds were prepared using tandem [4+2] cycloaddition/deamination between azabutadiene and dienophiles.  相似文献   
33.
34.
A theoretical study at the Hartree–Fock and density functional theory levels is performed on sulfonamide‐type bacteriostatic compounds with the aim to provide an insight into their structure–activity relationship. The basicity of the p‐amino group is analyzed by means of the proton affinities and the protonation energies, showing that molecules presenting bacteriostatic activity are less basic, i.e., they are characterized by larger protonation energies and smaller proton affinities. The acidity of the amide group is analyzed through the deprotonation energy. The results reveal that the more acidic molecules present a larger bacteriostatic activity. This result is also confirmed from a study of bond orders. A bond order analysis of the amide group suggests that the electron attracting group in these molecules is responsible for the increase in acidity. The charge of the SO2 group is also shown to be affected by the presence of the electron attracting group and consequently related to the acidity of the molecules. A geometric analysis shows that structures in which the amino group is more coplanar with respect to the benzenic ring possess larger bacteriostatic activity. A conformational analysis of these molecules illustrates that active molecules have relatively larger torsion energy barriers. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 165–172, 2003  相似文献   
35.
Immunoassays are one of the most convenient methods for environmental monitoring, but have been limited so far by low yield and low affinity antibodies (Abs). With the advent of recombinant Ab (rAb) technology and the expression of these Abs in organisms such as yeast, bacteria, insects and plants, widespread monitoring of our food and environment for organic contaminants using immunoassays has become feasible. A multitude of immunoassays have been developed to detect pesticides in soils, ground and river water, foods and biological samples, such as urine and semen. In this paper, we describe advances in Ab production, the move away from using animals, phage-display technologies and the advent of plant-derived Ab expression systems. Finally, we describe future possibilities in Ab technology for environmental monitoring.  相似文献   
36.
Several biaryls bearing various substituents on both rings were synthesized in a preparative fashion, and in yields up to 88% by a technical improvement on the classical Ullmann reaction. All these biaryls bear reactive functional groups (i.e. formyl, methoxycarbonyl, dimethoxycarbonylpropyl and butanolidylmethyl) in both the o and o′ positions. The biaryls 9, 13, 21 and 26–33 are plausible synthons for bisbenzocyclooctadiene lignans such as schizandrin and steganacin.  相似文献   
37.
In the context of a European project, a new approach of sampling of volatile polycyclic aromatic hydrocarbons (PAHs) from air was developed. In fact, the aim of this project was to test the efficiency of an air cleansing prototype reactor, which was operating by non-thermal plasmolysis. With an eye to model the atmosphere ejected by the prototype, we needed to vaporise the volatile PAHs in an air stream at concentrations as low as those recommended by European Directives (96/62/CE) for PAHs in ambient air (i.e. 1 ng m−3). Our strategy was based on the analysis of PAHs trapped in an aqueous medium, in order to avoid important losses of volatile compounds observed during the delicate desorption-concentration step when classical solid supports are used. Then a study was carried out to determine: the design of the collecting part, the flow-rate of the air sampling, the nature and concentration of chemical additives used to enhance PAH solubility in water. The very highly diluted aqueous media obtained after the bubbling step were concentrated by solid-phase extraction (SPE) on hydrophobic cartridges and analysed on-line by reversed-phase HPLC with UV and fluorimetric detections. Lastly, the sampling technique was directly applied to the outlet of the air cleansing prototype and the analysis after 3-6 h of non-thermal plasmolysis showed that the target volatile PAHs were not present in an air stream initially polluted by volatile organic compounds.  相似文献   
38.
The atomistic origin of fatigue failure in micron-sized silicon devices is not fully understood. Two series of density-functional theory calculations on cubic diamond Si explore the effect of surface bond formation on crack healing in systems which exhibit strong surface reconstruction. Both series introduce a separation between Si(100) layers (i.e., the crack) and allow the ions to relax to their minimum-energy configuration. The initial surface ionic positions are either bulk terminated or 2 x 1 reconstructed. A plot of the energy versus the introduced separation reveals that once the surfaces reconstruct, the crack is no longer able to return to the equilibrium configuration. Rather, the healed crack interface contains defects which places the flawed energy minimum at a finite strain of 3% and an increased energy of 1.13 Jm2 relative to the equilibrium configuration. The irreversible plastic deformation supports the mechanism proposed by Kahn et al. [Science 298 1215 (2002)] that invokes mechanically induced subcritical cracking to explain the delayed onset of failure.  相似文献   
39.
A total synthesis of (-)steganone, correlating it with L-glutamic acid, shows it to have the opposite configuration to that assigned by Kupchan.  相似文献   
40.
The acidity functions of aqueous trifluoroacetic and trifluoromethanesulphonic acid mixtures, and aqueous hexafluoropropane-2, 2-diol solutions, have been determined by differential pulse polarography. The apparent shift of the half-wave potential for the ferrocene—ferricinium couple, as the solvent composition is changed, is used to indicate the change in potential of a glass electrode; acidity is measured as the HGF acidity function. The densities of two of these solvent systems as a function of composition are also reported. Trifluoromethanesulphonic acid—water mixtures represent the strongest aqueous acid solvent system so far studied.  相似文献   
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