全文获取类型
收费全文 | 1793篇 |
免费 | 69篇 |
国内免费 | 10篇 |
专业分类
化学 | 1207篇 |
晶体学 | 15篇 |
力学 | 36篇 |
数学 | 250篇 |
物理学 | 364篇 |
出版年
2023年 | 21篇 |
2022年 | 27篇 |
2021年 | 42篇 |
2020年 | 30篇 |
2019年 | 46篇 |
2018年 | 37篇 |
2017年 | 30篇 |
2016年 | 55篇 |
2015年 | 49篇 |
2014年 | 55篇 |
2013年 | 100篇 |
2012年 | 100篇 |
2011年 | 141篇 |
2010年 | 75篇 |
2009年 | 89篇 |
2008年 | 104篇 |
2007年 | 96篇 |
2006年 | 102篇 |
2005年 | 103篇 |
2004年 | 60篇 |
2003年 | 57篇 |
2002年 | 68篇 |
2001年 | 26篇 |
2000年 | 31篇 |
1999年 | 20篇 |
1998年 | 14篇 |
1997年 | 15篇 |
1996年 | 19篇 |
1995年 | 20篇 |
1994年 | 18篇 |
1993年 | 18篇 |
1992年 | 10篇 |
1991年 | 15篇 |
1990年 | 11篇 |
1989年 | 11篇 |
1988年 | 12篇 |
1986年 | 15篇 |
1985年 | 11篇 |
1984年 | 18篇 |
1983年 | 13篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 9篇 |
1979年 | 10篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1976年 | 5篇 |
1975年 | 7篇 |
1974年 | 6篇 |
1970年 | 5篇 |
排序方式: 共有1872条查询结果,搜索用时 15 毫秒
21.
Diaz-Herrera E Ramirez-Santiago G Moreno-Razo JA 《The Journal of chemical physics》2005,123(18):184507
We have carried out extensive equilibrium molecular-dynamics simulations to study quantitatively the topology of the temperature versus density phase diagrams and related interfacial phenomena in a partially miscible symmetric Lennard-Jones binary mixture. The topological features are studied as a function of miscibility parameter, alpha = epsilonAB/epsilonAA. Here epsilonAA = epsilonBB and epsilonAB stand for the parameters related to the attractive part of the intermolecular interactions for similar and dissimilar particles, respectively. When the miscibility varies in the range 0 < alpha < 1, a continuous critical line of consolute points Tcons(rho)--critical demixing transition line--appears. This line intersects the liquid-vapor coexistence curve at different positions depending on the values of alpha, yielding mainly three different topologies for the phase diagrams. These results are in qualitative agreement to those found previously for square-well and hard-core Yukawa binary mixtures. The main contributions of the present paper are (i) a quantitative analysis of the phase behavior and (ii) a detailed study of the liquid-liquid interfacial and liquid-vapor surface tensions, as function of temperature and miscibility as well as its relationship to the topological features of the phase diagrams. 相似文献
22.
A.G. Gonzalez J.M. Arteaga J.J. Fernandez J.D. Martin M. Norte J.Z. Ruano 《Tetrahedron》1984,40(14):2751-2755
The structures of three brominated terpenoids which are natural products from the red alga Laurencia pinnatifida (Gmal. Lamour) are described. The structures of the sesquiterpenes and were determined by spectral comparison and chemical interconversion. The structure of the squalene-derived terpenoid was secured by chemical transformation into thyrsiferol, a brominated triterpene previously isolated from the red alga Laurencia thyrsifera. 相似文献
23.
Valenzuela-Calahorro C Cuerda-Correa E Navarrete-Guijosa A Gonzalez Pradas E 《Journal of colloid and interface science》2002,248(1):33-40
The knowledge of the adsorption processes of nonelectrolytes from liquid solution on solid materials involves the study of their kinetic and equilibrium aspects as well as the understanding of their thermodynamic functions. However, in most published papers adsorption isotherms are analyzed by using the Giles classification and other proposed equations which are either empirical or based on kinetic or thermodynamic criteria. Our opinion is that both the kinetic and the equilibrium studies must be complementary and that, in general, equations describing the adsorption isotherms come from the kinetic laws governing the different partial processes which determine the global process. These kinetic laws may be derived from single models. In this paper a single model is proposed, which makes it possible to establish a kinetic law satisfactorily fitting a great number of C (concentration) vs t (time) isotherms. This model has been applied to study the adsorption process of prednisolone by six carbonaceous materials from ethanol solution, the specific adsorption rate, and the activation thermodynamic functions being calculated. The results obtained have also been used to analyze the influence of the intraparticle diffusion on the kinetics of the process. 相似文献
24.
General indole C3 reductive alkylation conditions have been developed. The scope of this reaction includes C2 unsubstituted indoles, aryl and alkyl aldehydes, as well as N-H and N-alkyl indole substrates. 相似文献
25.
Pérez-Mendoza M Gonzalez J Wright PA Seaton NA 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7653-7658
We have measured the adsorption of methane and ethane to high pressure on SBA-2, a structured mesoporous silica composed of spheres connected by narrow channels. The experimental data were analyzed by carrying out Monte Carlo simulations of adsorption in pore structure models of different complexity and then adjusting the parameters of the models to match the Monte Carlo results to the experimental data. We found that a model based on single-sized spherical cavities was inadequate and that it is necessary to explicitly account for the interconnecting channels. Further, we found that despite the basic regularity of the SBA-2 structure, it is necessary to allow for a distribution of the sizes of both the cavities and the channels. These size distributions were obtained by fitting the parameters of the model to the experimental adsorption data, revealing detailed structural information not previously known for this material. The channels were found to be 5-15 A in diameter, while the cavities were 40-50 A in diameter. There is some evidence that the distribution of channel sizes leads to a percolation effect whereby the pore structure is not equally accessible to all adsorptives. 相似文献
26.
Laser ablation in analytical chemistry-a review 总被引:4,自引:0,他引:4
Laser ablation is becoming a dominant technology for direct solid sampling in analytical chemistry. Laser ablation refers to the process in which an intense burst of energy delivered by a short laser pulse is used to sample (remove a portion of) a material. The advantages of laser ablation chemical analysis include direct characterization of solids, no chemical procedures for dissolution, reduced risk of contamination or sample loss, analysis of very small samples not separable for solution analysis, and determination of spatial distributions of elemental composition. This review describes recent research to understand and utilize laser ablation for direct solid sampling, with emphasis on sample introduction to an inductively coupled plasma (ICP). Current research related to contemporary experimental systems, calibration and optimization, and fractionation is discussed, with a summary of applications in several areas. 相似文献
27.
X. Assfeld M. F. Ruizlopez J. Gonzalez R. Lopez J. A. Sordo T. L. Sordo 《Journal of computational chemistry》1994,15(5):479-487
The effect of correlation energy, basis set size, zero-point energy (ZPE) correction, and solvation on the reaction mechanism of the ketene–imine cycloaddition reaction has been investigated. The electrostatic solvent effect was studied with a self-consistent reaction field method in which the solvation energy is obtained using a multipole expansion of the molecular charge distribution. The ab initio results have been analyzed by means of a theoretical method based on the expansion of the MOs of the supermolecule in terms of those of the reactants and the performance of the configuration analysis. In gas phase, due to the correlation energy and/or the ZPE corrections, the reaction is predicted to be a one-step process. In solution, the stabilization of the charge-transferred configurations results in the occurrence of a very stable, Zwitterionic intermediate giving a two-step mechanism. © 1994 by John Wiley & Sons, Inc. 相似文献
28.
García-Orozco I López-Cortés JG Ortega-Alfaro MC Toscano RA Penieres-Carrillo G Alvarez-Toledano C 《Inorganic chemistry》2004,43(26):8572-8576
The paper describes the synthesis and structural characterization of four novel copper(I) complexes [CuL(PPh(3))(2)] (L = 3-hydroxy-3-(p-R-phenyl)-2-propenedithioate). In addition, a tautomeric equilibrium in solution was found and Hammett correlations with (13)C NMR parameters were studied. The structure of one complex was fully established by X-ray diffraction analysis. 相似文献
29.
The reaction of several α-amino acids and peptides (containing Gly, L-Ala, L-Leu, L- or DL-Phe, and/or L- or D-Val) with air-diluted nitrogen oxides has been studied to roughly mimic the N-nitrosation of peptide bonds that the contaminated urban air might produce in pulmonary tissues. Most N-protected α-amino acids give practically quantitative yields of N-nitroso derivatives. N-Protected dipeptides afford either dinitrosated peptides, mixtures of di- and mononitrosated compounds, selectively mononitrosated products, or no reaction at all, depending mainly on steric effects. The same trends are observed for some higher peptides. The (po1y)nitrosated Peptides, which retain the chirality of the starting materials, have been characterized by 1H and 13C NMR spectroscopy and are cleaved by pyrrolidine and amino esters under mild conditions to give (new) amides or peptides plus diazo derivatives. 相似文献
30.
Lpez Susana Owen Guillermo Saboya Martha 《Central European Journal of Operations Research》2022,30(3):837-859
Central European Journal of Operations Research - Standard approaches to model interaction networks are limited in their capacity to describe the nuances of real communication. We present a game... 相似文献