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排序方式: 共有794条查询结果,搜索用时 187 毫秒
61.
Mihaela Gulea Małgorzata Kwiatkowska Piotr Łyżwa Remi Legay Annie-Claude Gaumont Piotr Kiełbasiński 《Tetrahedron: Asymmetry》2009,20(3):293-297
The Michael addition of selected sulfur and nitrogen nucleophiles to a chiral non-racemic 2-phosphono-2,3-didehydrothiolane S-oxide is fully diastereoselective. The enantiomeric excesses of the adducts obtained could be determined by 31P NMR spectroscopy using (R)-(+)-tert-butyl(phenyl)phosphinothioic acid as a chiral solvating agent. The addition of thiophenol was monitored by 31P NMR spectroscopy which made it possible to observe the formation and evolution of the kinetic and thermodynamic adducts in the reaction mixture. The structures of both enantiomeric thiophenol adducts have been determined by X-ray analysis. 相似文献
62.
Azide ions (5–120 μg) are oxidized by cerium(IV) in an acidic medium. The nitrogen evolved is displaced by helium carrier and quantified by gas chromatography with a thermal conductivity detector. The relative standard deviation is <5%. Many sulphur anions, cyanide and some metal ions which form azide complexes do not interfere. 相似文献
63.
Explicit results of the van der Pauw method for a sample containing an isolated hole are presented together with experimental confirmation. Results of measurements and numerical analysis strongly suggest that four probe resistivities obey inequality similar in the form to the famous van der Pauw equation. The inequality seems to be valid for any sample with an isolated hole and contacts located on the same edge, however rigorous proof is not given. The inequality can be used for experimental detection of the sample quality. 相似文献
64.
P. Borys Z. J. Grzywna J. Łuczka 《The European Physical Journal B - Condensed Matter and Complex Systems》2011,83(2):223-233
We consider a deterministic process described by a discrete one-dimensional chaotic map and study its diffusive-like properties. Starting with the corresponding Frobenius-Perron equation we derive an approximate evolution equation for the probability distribution which is a partial differential equation of a hyperbolic type. Consequently, the process is correlated, non-Markovian, non-Gaussian and the information propagates with a finite velocity. This is in clear contrast to conventional diffusion processes described by a standard parabolic diffusion equation with an infinite velocity of information propagation. Our approach allows for a more complete characterisation of diffusion dynamics of deterministic systems. 相似文献
65.
M?ssbauer effect experiments in scattering geometry were performed for gauging plates and bearings in order to measure the retained austenite content. The results, obtained from numerical calculations of Mössbauer spectra are compared with the X-ray diffraction measurements. A simple three point Mössbauer effect technique is applied in order to decrease the time of measurements in the industrial use. 相似文献
66.
The comparative analysis of IR and Raman spectra of peramine and its four derivatives in solid state was carried out. The harmonic vibrational frequencies, infrared intensities, and Raman scattering activities were calculated at density functional B3LYP methods with 6-311++G(d,p) basis set. For the predicted spectra, a potential energy distribution of normal modes was also calculated. For peramine derivatives the conjugation effect of pyrrole with pyrazinone ring was observed as a result of introduction of double bond. Moreover, 1H NMR analysis indicated that pyrrole protons are deshielded in comparison with the pyrrolopyrazinone model ring system. 相似文献
67.
I. Fuks-Janczarek Jean Ebothe R. Miedziński R. Gabański A. H. Reshak M. Łapkowski R. Motyka I. V. Kityk J. Suwiński 《Laser Physics》2008,18(9):1056-1069
A new promising organic chromophore for two-photon laser absorption at 1064 nm with 1,4-diethoxy-2,5-bis[2-(5-methylthien-2-yl)ethenyl]benzene (A-C) was synthesized. We have performed evaluations of the two-photon absorption for these chromophores incorporated into the polymer matrices. Following the obtained quantum chemical data, we have performed quantum chemical simulations of the third-order susceptibilities for the investigated chrompophore incorporated into the PMMA matrices. The calculations were done within the three-level model. We have established that the experimentally calculated data are a bit less than theoretically calculated; however, the general tendency of their changes shows a good coincidence. The maximally achieved value of the TPA is equal to about 59.2 cm/GW at wavelength 1064 nm, which, together with their high photothermal stabilities, make them good candidates for optical-limiting processes. 相似文献
68.
E. Łodyga-Chruścińska S. Ołdziej D. Sanna G. Micera L. Chruściński K. Kaczmarek R.J. Nachman J. Zabrocki A. Sykuła 《Polyhedron》2009
Spectroscopic data, including electronic absorption, CD and EPR results, as well as theoretical calculations have shown that the insertion of 4-aminopyroglutamate, a novel cis-peptide bond mimic, in the insect kinin peptide leads to an effective ligand towards Cu(II) ions at basic pH ranges. The 4-aminopyroglutamate motif induces a specific peptide conformation which favors the formation of one or two five-membered chelating rings stabilizing a bent structure, with the coordination of 3N-type or 4N-type in the metallopeptide molecule involving in metal bonding C-terminal of modified peptide. It is worth noting that the copper(II) bonding does not undergo hydrolysis even at a very high pH range. 相似文献
69.
Albrecht Ł Ransborg LK Gschwend B Jørgensen KA 《Journal of the American Chemical Society》2010,132(50):17886-17893
The first enantioselective methodology for the synthesis of electron-poor 2-hydroxyalkyl- and 2-aminoalkyl furanes is demonstrated in this study. It utilizes a highly stereoselective organocatalytic one-pot reaction cascade: epoxidation or aziridination of α,β-unsaturated aldehydes followed by Feist-Be?nary reaction of various 1,3-dicarbonyl compounds to give the target furanes. This efficient multibond forming reaction cascade benefits from low catalyst loadings and readily available starting materials. Furthermore, the possibility to interrupt the reaction sequence at the stage of the corresponding optically active 2-hydroxyalkyl- and 2-aminoalkyl 2,3-dihydrofuranes with three stereogenic centers is also presented. Finally, models which account for the formation of the optically active 2,3-dihydrofuranes are proposed. 相似文献
70.
Angelika Baranowska Krzysztof Z. Ła̧czkowski Andrzej J. Sadlej 《Journal of computational chemistry》2010,31(6):1176-1181
We have carried out extensive studies on the basis set dependence of the calculated specific optical rotation (OR) in molecules at the level of the time–dependent Hartree–Fock and density functional approximations. To reach the limits of the basis set saturation, we have devised an artificial model, the asymmetrically deformed (chiral) methane (CM) molecule. This small system permits to use basis sets which are prohibitively large for real chiral molecules and yet shows all the important features of the basis set dependence of the OR values. The convergence of the OR has been studied with n‐aug‐cc‐pVXZ basis sets of Dunning up to the 6–ζ. In a parallel series of calculations, we have used the recently developed large polarized (LPolX) basis sets. The relatively small LPolX sets have been shown to be competitive to very large n‐aug‐cc‐pVXZ basis sets. The conclusions reached in calculations of OR in CM concerning the usefulness of LPolX basis sets have been further tested on (S)‐methyloxirane and (S)‐fluoro‐oxirane. The smallest set of the LPolX family (LPol–ds) has been found to yield OR values of similar quality as those obtained with much larger Dunning's aug‐cc‐pVQZ basis set. These results have encouraged us to carry out the OR calculations with LPol–ds basis sets for systems as large as β‐pinene and trans‐pinane. In both cases, our calculations have lead to the correct sign of the OR value in these molecules. This makes the relatively small LPol–ds basis sets likely to be useful in OR calculations for large molecules. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献