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91.
The asymmetric organocatalytic α-sulfenylation of substituted piperazine-2,5-diones is reported, with cinchona alkaloids as chiral Lewis bases and electrophilic sulfur transfer reagents. Catalyst loadings, the type of sulfur transfer reagent, temperature, and solvent were investigated in order to optimize the reaction conditions. The effects of ring substitution and the type of catalyst on the yield and enantioselectivity of the reaction are reported.  相似文献   
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94.
The decomposition of methylene blue (MB) in aqueous solution was investigated using a pulsed corona discharge. The discharge was ignited in the gas bubbled in the solution through several needle electrodes. The influence of treatment time, volume of the treated solution and initial concentration of the dye in solution on MB degradation was studied. The effect of the nature of the gas introduced was also investigated. For the same energy input, MB conversion increased in the order air < argon < oxygen. When using oxygen, the decomposition of MB exceeded 95% after ~20 min plasma treatment. Higher efficiency was obtained for higher treated volume and higher initial concentration. At 90% conversion the yield obtained with oxygen was ~5 g/kWh for an initial concentration of 150 mg/l and a treated volume of solution of 100 ml.  相似文献   
95.
The paper is concerned with light scattering studies on solutions of ultrahigh molecular weight poly(butyl methacrylate). The dependence of the radius of gyration and of the second virial coefficient on the weight-average molecular weight of the polymers was established in methyl ethyl ketone, dimethylformamide, and CCl4. Short-range and long-range interactions were discussed in terms of the steric factor σ, of the interaction parameter B, and of the interpenetration function ψ(z).  相似文献   
96.
The problem of eigenvalues of the collision operator for a gas of acoustic phonons scattered by point mass defects of small concentration embedded in transversely isotropic media is considered. For this purpose the properties of solution of the Boltzmann-Peierls kinetic equation for spatially homogeneous states are studied. An analytic formula for the Laplace transform of the distribution function is obtained. The singularities of this Laplace transform and the initial distribution function determine the dependence of this distribution function on time. For several hexagonal materials characteristics of the singularity set are calculated. Usually the singularity set consists of a continuous part and four discrete points. However, there exist elastic hexagonal materials (4He, Cd, Ta, Zn) for which some of discrete points are absent. For some materials (e.g. Zr) the continuous part is very narrow.  相似文献   
97.
The synthesis, the X-ray, NMR and molecular modeling structure determination of a new orthopara[4.4]cyclophane are reported. The similarity of the π(CO)-π(Ar) driven conformational equilibrium of this compound to the work of an amusement ride machinery is also revealed.  相似文献   
98.
The synthesis of novel azofunctional oligoesters through bulk ring opening of ε‐caprolactone and D ,L ‐lactide (LA) at 100 and 130 °C, respectively, mediated by N‐ethyl‐N‐(2‐hydroxyethyl)‐4‐(4‐nitrophenylazo)aniline (Disperse Red 1) (DR1) is described. The synthetic procedure allows “clean” products because no catalysts were used in the reaction. Moreover, DR1 moiety is showed for the first time to promote the ring opening of cyclic esters. The molecular structure of the obtained oligoesters was established by NMR spectroscopy, MALDI ToF MS and electrospray ionization mass spectrometry (ESI MS). ESI‐MS/MS fragmentation experiments were used to demonstrate the nature of the chain end groups (hydroxyl and DR1). Intermolecular transesterification reactions were proved by mass spectrometry studies at least in the case of LA oligomerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 534–547, 2009  相似文献   
99.
Direct simulations of macromolecular fluids are carried out for flows between parallel plates and in expanding and contracting channels. The macromolecules are modeled as FENE dumbbells with soft disks or Lennard-Jones dumbbell-dumbbell interactions. The results are presented in terms of profiles and contour plots of velocity, pressure, temperature, density, and flow fields. In addition the data for potential energy, shear stress, and the normal components of the stress tensor are collected. In general, an excellent agreement is found between the simulated profiles and the well-known flow structures, such as flow separation and formation of viscous eddies, indicating that micro-hydrodynamics is a viable tool in linking macroscopic phenomena with the underlying physical mechanisms. The simulations are performed in the Newtonian regime, for medium-size systems comprising up to 3888 dumbbells. This number is sufficiently large to control boundary and particle number effects. The flow is induced by gravity. The traditional stochastic (thermal) and periodic boundary conditions are employed. Also, diffusive boundary conditions, which could include a stagnant fluid layer and repulsive potential walls, are developed. The scaling problems, which are related to the application of a large external force in a microscopic system (of the size of the order 100 Å), result in extreme pressure and temperature gradients. In addition, the viscosity and thermal conductivity coefficients obtained from velocity and temperature profiles of the channel flow are presented. These results are confirmed independently from modeling of Couette flow by the SLLOD equations of motion and from the Evans algorithm for thermal conductivity.  相似文献   
100.
The immobilization of acetylcholinesterase on platinum microelectrodes modified with p-nitrobenzenediazonium is optimized. In the first step, a layer of p-nitrophenyl groups was deposited on the surface and then reduced to p-aminophenyl groups. Finally, the enzyme was linked to the amino groups on the surface using glutaraldehyde. Each step of the electrode modification was characterized by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) at acidic and neutral pH to modify the electric charges of different bound moieties. The deposition of diazonium groups was attempted by potentiometry, amperometry or CV, but only potentiometry proceeded without passivation of the surface. The use of microelectrodes improved the limit of detection of ethylparaoxon measurements to 20 nM (compared to 100 nM in case of screen-printed electrodes based on the same method of immobilization). The method allowed the production of stable and reproducible amperometric microbiosensors and may be adapted to other enzymes and electrode materials.  相似文献   
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