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81.
The influence of Mm (Mm=mischmetal) substitution and hydrogen absorption on the magnetic properties of Ho1−xMmxCo2 (x=0, 0.1, 0.2, 0.3 and 0.4) alloys have been determined through the temperature dependence of ac susceptibility and thermopower measurements. The changes in magnetic-ordering temperature of Ho1−xMmxCo2 alloys have been explained based on the dilution of the magnetic ions and weakening of 4f–3d exchange interactions. The gradual disappearance of the magnetic transition temperature upon increasing hydrogen concentration (y) has been interpreted by the lattice expansion and charge transfer between absorbed hydrogen and 3d-band of Ho1−xMmxCo2. 相似文献
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Zinc salts of carboxylic acids, phenols and alcohols are found to react with tertiary alkyl halides in nonpolar solvents and in presence of a base yielding the corresponding esters and ethers in moderate to good yields. 相似文献
84.
Aqua dissociation nature of cesium hydroxide 总被引:1,自引:0,他引:1
To understand the mechanism of aqueous base dissociation chemistry, the ionic dissociation of cesium-hydroxide in water clusters is examined using density functional theory and ab initio calculations. In this study, we report hydrated structures, stabilities, thermodynamic quantities, dissociation energies, infrared spectra, and electronic properties of CsOH(H(2)O)(n=0-4). With the addition of water molecules, the Cs-OH bond lengthened significantly from 2.46 A for n=1 to 3.08 A for n=4, which causes redshift in Cs-O stretching frequency. It is found that three water molecules are needed for the dissociation of Cs-OH, in contrast to the case of strong acid dissociation which requires at least four water molecules. However, the dissociation for n=3 could be considered as incomplete because a very weak CS em leader OH stretch mode is still present, while that for n=4 is complete since the Cs em leader OH mode no longer exists. This study can be related with hydration chemistry of cations and anions, and extended into the intra- and intercharge-transfer phenomena. 相似文献
85.
June Cyriac Justin Paulose Mathai George Marupaka Ramesh Ragampeta Srinivas Daryl Giblin Michael L. Gross 《Journal of the American Society for Mass Spectrometry》2014,25(3):398-409
ESI-protonated 1,5-bis-(2-methoxyphenyl)-1,4-pentadien-3-one (1) undergoes a gas-phase Nazarov cyclization and dissociates via expulsions of ketene and anisole. The dissociations of the [M + D]+ ions are accompanied by limited HD scrambling that supports the proposed cyclization. Solution cyclization of 1 was effected to yield the cyclic ketone, 2,3-bis-(2-methoxyphenyl)-cyclopent-2-ene-1-one, (2) on a time scale that is significantly shorter than the time for cyclization of dibenzalacetone. The dissociation characteristics of the ESI-generated [M + H]+ ion of the synthetic cyclic ketone closely resemble those of 1, suggesting that gas-phase and solution cyclization products are the same. Additional mechanistic studies by density functional theory (DFT) methods of the gas-phase reaction reveals that the initial cyclization is followed by two sequential 1,2-aryl migrations that account for the observed structure of the cyclic product in the gas phase and solution. Furthermore, the DFT calculations show that the methoxy group serves as a catalyst for the proton migrations necessary for both cyclization and fragmentation after aryl migration. An isomer formed by moving the 2-methoxy to the 4-position requires relatively higher collision energy for the elimination of anisole, as is consistent with DFT calculations. Replacement of the 2-methoxy group with an OH shows that the cyclization followed by aryl migration and elimination of phenol occurs from the [M + H]+ ion at low energy similar to that for 1. Figure
The role of methoxy group in the Nazarov cyclization of 1,5-bis-(2-methoxyphenyl)-1,4-pentadien-3-one in the gas-phase and condensed phase by June Cyriac, Justin Paulose, M. George, Department of Chemistry, Sacred Heart College, Thevara, Cochin, Kerala, India-682013., M. Ramesh, R. Srinivas, National center for Mass Spectrometry, IICT, Hyderabad, India. Daryl Giblin and Michael L. Gross, Department of Chemistry, Washington University in St.Louis, St.Louis, USA, MO 63130. 相似文献
86.
Sudhakar Chaudhary V. V. K. Srinivas Kumar 《Numerical Functional Analysis & Optimization》2013,34(3):264-283
The objective of this article is to discuss the existence and the uniqueness of a weighted extended B-spline-(WEB-spline) based discrete solution for the Maxwell equations in low frequency limit. The domain is composed of insulating and conducting regions. This problem has saddle point structure where the electric field in insulating region is the Lagrange multiplier that forces curl-free constraint on the magnetic field. 相似文献
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Srinivas Pasikanti D. Srinivasa Reddy P.K. Dubey Parthasarathi Das 《Tetrahedron letters》2010,51(1):151-152
Synthesis of varenicline the antismoking drug has been achieved in six steps with 10% overall yield. A Diels-Alder reaction, oxidative cleavage of an olefin and reductive amination remain as key steps in the synthesis 相似文献