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61.
Ludvík Beneš Klára Melánová Vítězslav Zima Jaroslava Kalousová Jiří Votinský 《Journal of inclusion phenomena and macrocyclic chemistry》1998,31(3):275-286
Recent knowledge of the kinetics and intercalation mechanisms are summarized and accompanied by examples of intercalation reactions of water and ethanol into anhydrous vanadyl phosphate and redox intercalation of alkali metal cations into vanadyl phosphate dihydrate. Three possible mechanisms of intercalation are presented which are based on: (i) a concept of exfoliation of layers; (ii) the formation of stages and randomly stacked layers; (iii) co-existence of intercalated and non-intercalated parts of crystals of the host separated by an advancing phase boundary. The corresponding kinetic curves are ascribed to mechanisms (ii) and (iii). 相似文献
62.
Laure Gouriou Štěpán Vysko?il Pavel Ko?ovský 《Journal of organometallic chemistry》2003,687(2):525-537
The reaction of iso-cinnamyl acetate with NaC(Me)(CO2Me)2, catalysed by Pd-‘MOP’ (MOP=2-methoxy-2′-diphenylphosphino-1,1′-binaphthalene) is known to proceed with a regiochemical memory effect that results in the predominant generation of the branched alkylation product. The analogous reaction employing ‘MAP’ as ligand (MAP=2-N,N-dimethylamino-2′-diphenylphosphino-1,1′-binaphthalene) proceeds with ‘normal’ regioselectivity to generate predominantly the linear isomer of product. A 2H-NMR based analysis, employing quadrupolar coupling in a chiral liquid crystal matrix, has been developed to facilitate the simultaneous study of the regiochemical and stereochemical outcome of the reaction of both enantiomers of iso-cinnamyl ester substrates in 2H-labelled but racemic samples. The analysis allows the comparison of relative rates of two competing isomerisation processes occurring in the π-allyl intermediates in the Pd-catalysed reaction, one of which facilitates asymmetric induction, the other resulting in loss of regiochemical memory. It is demonstrated that the two processes are partially coupled and that this then limits the attainment of high global enantiomeric excess in the branched product to reactions that proceed with low regiochemical retention. A key factor for the observation of high regiochemical memory is found to be the nucleophilicity of the malonate anion and the electrophilicity of the Pd-π-allyl intermediate with reduction in the reactivity of either partner resulting in the onset of substantial loss of memory. 相似文献
63.
A classical electrostatic polarization scheme using the additive distribution procedure has been applied to determine the longitudinal polarizability of an all-trans hexatriene molecule in an infinite stretched fiber. The parameters have been derived from ab initio CPHF/6-31G calculations and the electrostatic scheme has been validated via comparison with ab initio results on small clusters. Upon packing the polarizability of all-trans hexatriene increases by 7%. This small increase results from the balance between the enhancement of the polarizability due to collinear packing and the reduction associated with lateral packing. 相似文献
64.
A theoretical model of the evaporation of a pure liquid layer is developed. We focus on the influence of an inert gaseous component, in addition to vapor, on surface-tension-driven Bénard instabilities. It is assumed that the gas phase is perfectly mixed at some distance from the liquid-gas interface (given composition, pressure, and temperature). If this distance is not much larger than the liquid layer thickness, it is shown that a reduction of the full two-layer problem to a one-layer problem is possible, provided the evaporation rate is not too large. An analytical expression is given for the corresponding dimensionless heat transfer coefficient (a generalized, wavenumber-dependent Biot number) at the evaporating interface. The approach is validated through a comparison with a direct numerical resolution of the full two-layer problem. 相似文献
65.
Fullerenes have unique structural and electronic properties that make them attractive candidates for diagnostic, therapeutic, and theranostic applications. However, their poor water solubility remains a limiting factor in realizing their full biomedical potential. Here, we present an approach based on a combination of supramolecular and covalent chemistry to access well-defined fullerene-containing polymer nanoparticles with a core–shell structure. In this approach, solvophobic forces and aromatic interactions first come into play to afford a micellar structure with a poly(ethylene glycol) shell and a corannulene-based fullerene-rich core. Covalent stabilization of the supramolecular assembly then affords core-crosslinked polymer nanoparticles. The shell makes these nanoparticles biocompatible and allows them to be dried to a solid and redispersed in water without inducing interparticle aggregation. The core allows a high content of different fullerene types to be encapsulated. Finally, covalent stabilization endows nanostructures with stability against changing environmental conditions.A polymer nanoparticle approach to biorelevant and robust fullerene nanoparticles is presented. 相似文献
66.
The present short review deals with electroanalytical aspects of electrochemical response of ascorbic acid (Vitamin C) at conducting and electrogenerated polymer modified electrodes. Two main topics are considered: (i) electrocatalytic oxidation of ascorbate at conducting polymer modified electrodes, leading to electroanalytical techniques for ascorbate assay, and (ii) retardation of ascorbate penetration through a layer of electrogenerated polymers, leading to permselective coatings and their diverse uses, especially for biosensing devices. 相似文献
67.
Homopolynuclear complexes of Cu(II) respectively Cr(III) with the glyoxylate dianion, C2H2O4
2-, have been studied in non-isothermal regime in air and nitrogen. The results of the non-isothermal analysis performed for
the synthesised complexes, Cu(C2H2O4)·0.5H2O, respectively [Cr2(OH)2(C2H2O4)2(OH2)4]·2H2O, correlated with the results of the IR and TG analysis of the compounds obtained by thermal treatment from the initial complexes
and the results of the GLC and XR analysis have led to the establishment of the thermal decomposition mechanisms for the two
studied complexes. The decomposition mechanisms confirm the stoichiometric and structural formulae proposed for the two synthesised
homopolynuclear complexes.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
68.
Ludvík Beneš Vítězslav Zima 《Journal of inclusion phenomena and macrocyclic chemistry》1994,20(4):381-391
The course of intercalation of water into 1-VOPO4 has been studied by thermomechanical analysis and X-ray diffraction. Neither formation of vanadyl phosphate monohydrate nor staging were observed during the intercalation. The broadening and the shift of the positions of the lines in the diffractograms have been explained by the random stacking of intercalated and nonintercalated layers in the sample. 相似文献
69.
V. Yu. Rovenskiî 《Siberian Mathematical Journal》1994,35(5):1027-1035
In Riemannian geometry and its applications, the most popular is the class of Riemannian submersions (and foliations) [1–4] which are characterized by simplest mutual disposition of fibers. The purpose of the present article is to introduce other, more general, classes of submersions of Riemannian manifolds which, as well as the class of Riemannian submersions, are described by simple local properties of configuration tensors and to begin their study.Given a submersion :MM of differentiable manifolds with compact connected fibers and any metric onM, we define a metric on the base with the help of theL
2-norm of horizontal fields. In this caseT¯ M becomes a subbundle of some larger bundleM. The main class of totally geodesic submersions introduced in the article (Definition 1) corresponds to the metrics onM with simplest disposition ofT¯ M inM. In the article we obtain a criterion for such submersions (Corollary 1); existence is proved by means of the product with a metric varying along fibers (Example 2). To study totally geodesic submersions, we use ideas from the theory of Riemannian submersions and submanifolds with degenerate second form (Theorems 1 and 2 and Corollary 4).Foliations modeled by totally geodesic submersions (see equality (13)) are of interest too, but we leave them beyond the scope of the article.This work was supported by the Russian Foundation for Fundamental Research (Grant 94-01-00271).Translated fromSibirskiî Matematicheskiî Zhurnal, Vol. 35, No. 5, pp. 1154–1164, September–October, 1994. 相似文献
70.
Mn2(CO)10 was photolysed in the gas phase by the XeCl-excimer laser with fluence in the range 25–300 mJ/cm2 and a dye laser. The UV/VIS emission of the products was probed on a nanosecond time scale. The emission from excited states of metal atoms was detected only. The Mn atoms are predominantly formed in their ground statea
6
S
2 1/2. The absorption of one photon and the subsequent relaxation process leads to the formation ofz
6
P
J
0
(J = 11/2, 21/2, 31/2) states and emission of photons at a wavelength of 403 nm. The formation of the excited statese
8
D
5 1/2,z
6
F
4 1/2
0
ande
6
D
4 1/2 and the subsequent emission observed at wavelengths of 357, 383 and 446 nm requires the absorption of two photons by the ground-state Mn atoms. In addition, transition from thea
6
D
j (J = 11/2, 21/2) lower states were observed in the wavelength-resolved Laser-Induced Fluorescence (LIF) spectra. 相似文献