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121.
An analysis of existing algebraic multiresonance spectroscopic Hamiltonians, derived by fitting to experimental data or from classical canonical or quantum Van Vleck perturbation theory, allows without any significant further classical or quantum calculation the assignment of quantum numbers and motions to states observed in spectra that were previously thought to be irregular or just unassignable. In such cases, inspection of the amplitude and phase of eigenfunctions previously calculated in the Hamiltonians derivation process but now transformed to a reduced dimension semiclassical action-angle representation reveals extremely simple albeit unfamiliar topologies that give quantum numbers by simply counting nodes and phase advances. The topology allows these simple wave functions to be sorted into dynamically different excitation ladders or classes of states which are associated with different regions of phase space. The rungs of these ladders or the states in the classes intersperse in energy causing the spectral complexity. No experimental procedure allows such sorting. The success of the work stems from (1) the qualitative insights of nonlinear dynamics, (2) the conversion of the quantum problem in full dimension to a semiclassical one in reduced dimension by use of a canonical transform that takes advantage of the polyad and other constants of the motion, and (3) the judicious choice of the reduced angle variables to reflect rational ratio resonance frequency conditions. This leads to localization of those semiclassical wave functions, which are affected by the particular resonance. In reverse, the localized appearance of the reduced dimension wave function reveals which resonances govern it and makes sorting visually simple. The success of the work also stems from (4) the revealing use of plots of phase advances as well as the usual densities of the eigenstates for sorting and assignment purposes. Even in classically chaotic regions, organizing trajectories, which correspond to averages over regional phase space structures that need not be computed, can easily be drawn as the structure about which eigenfunction localization takes place. The organizing trajectories when transformed back to the full dimensional configuration space reveal the internal molecular motions. The complexity of the usual quantum stationary and propagated wave functions and associated classical trajectories forbids most often such assignments and sorting. This procedure brings the ability to interpret complex vibrational spectra to a degree previously thought possible only for lower excitations. The new methodology replaces and extends the computationally more difficult parts of a procedure used by the authors that was applied successfully to several molecules during the past few years. The new methodology is applied to DCO, CHBrClF, and the bending of acetylene. 相似文献
122.
Lovrinovic M Fruk L Schröder H Niemeyer CM 《Chemical communications (Cambridge, England)》2007,(4):353-355
Site-specific bioconjugation of protein thioesters with a DNA oligonucleotide was achieved by Expressed Protein Ligation (EPL) and the new thiol group formed upon EPL in the conjugate was selectively coupled with small molecule labels using maleimide chemistry. 相似文献
123.
124.
An efficient method for the extraction of the carotenoids from Curtobacterium flaccumfaciens pvar poinsettiae was developed. The glucosides of C.p. 450 (=(all‐E,2R,2′R)‐2‐[4‐(β‐D ‐glucopyranosyloxy)‐3‐methylbut‐2‐enyl]‐2′‐(4‐hydroxy‐3‐methylbut‐2‐enyl)‐β, β‐carotene; 4 ) and of C.p. 473 (=(all‐E,2R,2′S)‐2‐[4‐(β‐D ‐glucopyranosyloxy)‐3‐methylbut‐2‐enyl]‐2′‐(3‐methylbut‐2‐enyl)‐3′,4′‐didehydro‐1′,2′‐dihydro‐β,ψ‐caroten‐1′‐ol; 5 ) were isolated for the first time. In addition, the hitherto unknown 3′,4′‐dihydro derivative of C.p. 450, called C.p. 460 (=(all‐E,2R,2′R)‐2‐(4‐hydroxy‐3‐methylbut‐2‐enyl)‐2′‐(3‐methylbut‐2‐enyl)‐1′,2′‐dihydro‐β,ψ‐caroten‐1′‐ol; 6 ), was identified. The structures were established by UV/VIS, CD, 1H‐ and 13C‐NMR, and mass spectra. 相似文献
125.
126.
In this paper we present different experiments describing the fabrication and characterisation of self-assembled monolayers of organothiols and also discuss some of the most important applications of these systems. The reader may practise the fabrication and characterisation of self-assembled monolayers with different endgroups by adsorption of CH3- and Oh-terminated alkanethiols on copper-coins (1 or 2 Pfenningcoins). Then patterned self-assembled monolayers of CH3- and OH-terminated alkanethiols are produced by applying the microcontact printing technique. When these gratings are wet with water-e.g. by breathing into the surfaces-the water adsorbs onto the hydrophilic OH-terminated areas but not on the hydrophobic CH3-terminated regions. Illumination with a laser then produces bright diffraction spots which disappear when the water evaporates. Finally, we briefly discuss applications of the self-assembled ultrathin films as sensor-devices and as substrates for CVD (chemical vapour deposition). 相似文献
127.
Christof M. Niemeyer Dietmar Blohm 《Angewandte Chemie (International ed. in English)》1999,38(19):2865-2869
The complete human genes (ca. 100 000) as well as the whole spectrum of biological diversity should soon be able to be analyzed simultaneously by means of DNA microarrays using the fast technical advances that are occurring in this area. The particular strength of array analysis, typically based on the hybridization of nucleic acid probes attached to microchips with labeled RNA or DNA samples, results from the highly redundant measurement of many parallel hybridization events (see picture), which leads to an extraordinary level of assay validation. 相似文献
128.
Burkhard Stahlmecke Sandra Wagener Christof Asbach Heinz Kaminski Heinz Fissan Thomas A. J. Kuhlbusch 《Journal of nanoparticle research》2009,11(7):1625-1635
The stability of agglomerates is not only an important material parameter of powders but also of interest for estimating the
particle size upon accidental release into the atmosphere. This is especially important when the size of primary particles
is well below the agglomerate size, which is usually the case when the size of primary particles is below 100 nm. During production
or airborne transportation in pipes, high particle concentrations lead to particle coagulation and the formation of agglomerates
in a size range of up to some micrometers. Binding between the primary particles in the agglomerates is usually due to van
der Waals forces. In the case of a leak in a pressurized vessel (e.g. reactor, transport pipe, etc.), these agglomerates can
be emitted and shear forces within the leak can cause agglomerates to breakup. In order to simulate such shear forces and
study their effect on agglomerate stability within the airborne state, a method was developed where agglomerate powders can
be aerosolized and passed through an orifice under various differential pressure conditions. First results show that a higher
differential pressure across the orifice causes a stronger fragmentation of the agglomerates, which furthermore seems to be
material dependent. 相似文献
129.
130.
Christof Schmitz Ahmed Mourran Helmut Keul Martin Möller Martina Keerl Walter Richtering 《Colloid and polymer science》2009,287(10):1183-1193
The effect of microstructure on the aggregation behaviour of symmetrical di- and triblock copolymers P(BMA)-b-P(MAA) and P(BMA)-b-P(BMA-co-MAA)-b-P(MAA) with a molecular weight of 40,000 g/mol was studied. The critical micelle concentration, hydrodynamic radius and morphology
of the micelles were determined by fluorescence spectroscopy, dynamic light scattering and scanning force microscopy (SFM).
Whereas no effect of the microstructure on the critical micelle concentration could be detected, the hydrodynamic radius decreased
from di- to triblock copolymer from 53 to 36 nm. The decrease of about 32% corresponds to the length of the random middle
block within the triblock copolymer so that the reduction in hydrodynamic radius was caused by a complete orientation of the
random middle block at the core corona interface. Finally, the SFM investigation showed that dehydration of micelles on a
substrate is accompanied by formation of a physisorbed monolayer with a thickness of 2 nm on which the micelles are deposited. 相似文献