全文获取类型
收费全文 | 2631篇 |
免费 | 89篇 |
国内免费 | 16篇 |
专业分类
化学 | 1790篇 |
晶体学 | 9篇 |
力学 | 85篇 |
数学 | 276篇 |
物理学 | 576篇 |
出版年
2023年 | 11篇 |
2022年 | 30篇 |
2021年 | 54篇 |
2020年 | 40篇 |
2019年 | 51篇 |
2018年 | 34篇 |
2017年 | 40篇 |
2016年 | 100篇 |
2015年 | 63篇 |
2014年 | 81篇 |
2013年 | 173篇 |
2012年 | 149篇 |
2011年 | 154篇 |
2010年 | 99篇 |
2009年 | 87篇 |
2008年 | 156篇 |
2007年 | 127篇 |
2006年 | 111篇 |
2005年 | 105篇 |
2004年 | 112篇 |
2003年 | 104篇 |
2002年 | 87篇 |
2001年 | 58篇 |
2000年 | 64篇 |
1999年 | 43篇 |
1998年 | 18篇 |
1997年 | 25篇 |
1996年 | 40篇 |
1995年 | 60篇 |
1994年 | 45篇 |
1993年 | 46篇 |
1992年 | 50篇 |
1991年 | 28篇 |
1990年 | 30篇 |
1989年 | 20篇 |
1988年 | 17篇 |
1987年 | 22篇 |
1986年 | 26篇 |
1985年 | 27篇 |
1984年 | 27篇 |
1983年 | 11篇 |
1982年 | 20篇 |
1981年 | 17篇 |
1980年 | 8篇 |
1979年 | 12篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1975年 | 6篇 |
1974年 | 8篇 |
1973年 | 8篇 |
排序方式: 共有2736条查询结果,搜索用时 406 毫秒
21.
O. G. Stradella S. A. Maluendes E. A. Castro A. H. Jubert 《Theoretical chemistry accounts》1987,72(1):57-62
By means of Bader's approach on topological properties of the electronic density, the major stability of the O-bonded adduct over the C-bonded one between MgF2 and CO is reinforced. 相似文献
22.
Prados-Rosales RC Herrera MC Luque-García JL de Castro L 《Journal of chromatography. A》2002,946(1-2):133-140
A fast microwave-assisted dansylation procedure has been developed for the derivatization of N-nitrosamines prior to high-performance liquid chromatography determination. N-Nitrosomorpholine, N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosopyrrolidine and N-nitrosopiperidine are first denitrosated by hydrobromic acid-acetic acid to produce secondary amines, which are then quantitatively dansylated in 5 min using radiation power of 378 W and a maximum pressure of 1.4 bar inside the reactor. The reaction mixture is separated on a C18 column with acetonitrile-water (55:45, v/v) as mobile phase with fluorimetric detection at 531 nm (excitation at 339 nm). The detection limits range from 8 to 75 pg for N-nitrosomorpholine and N-nitrosodiethylamine, respectively. The method was applied to study the recoveries of N-nitrosamines in beer and their determination in cigarette smoke. 相似文献
23.
Ana M. Reverdito Liliana Orelli Mnica Dalmaso Isabel Perillo Beatriz M. Fernndez 《Journal of heterocyclic chemistry》1991,28(2):273-281
Reaction of 1,2-diaryl-3-methyl-1,4,5,6-tetrahydropyrimidinium iodides 1a-i with alkaline solutions afforded N-aroyl-N-aryl-N'-methyltrimethylenediamines 2a-i . Compounds 2 are stable under acid conditions but in neutral or alkaline media spontaneously rearrange giving N-aroyl-N'-aryl-N-methyltrimethylenediamines 3a-i . Treating compounds 3 with concentrated acids reverse reaction takes place. Kinetic studies were performed on this intramolecular N → N' aroyl transfer over the Ho-pH range -0.9 to 2.30. Compounds 3 undergo acyl transfer to give 2 by a mechanism which involves a change in the rate determining step from formation to acid-catalysed decomposition of a six-membered heterocyclic intermediate on going from Ho to pH values. The existence of maxima in the pH rate profile allow to determine apparent pKa values of the hexahydropyrimidine intermediates which gave good correlation with the Swain F substituent constants. Stability of these heterocycles was also predicted by determination of thermodinamic parameters. Comparisons are made with the behaviour of five-membered heterocyclic intermediates (imidazolidine derivatives) which were studied in an earlier paper. 相似文献
24.
Zareen Ahkter Andrew J. Edwards Scott L. Ingham Jack Lewis Ana M. Martin Castro Paul R. Raithby Gregory P. Shields 《Journal of Cluster Science》2000,11(1):217-226
The reaction of the di-gold cation [Au2(dppx)]2+ with the heptanuclear cluster dianion [Os7(CO)20]2– affords the mixed metal cluster [Os7(CO)20{Au2(dppx)}] (x=m (1), e (2), b (3)). On standing, in solution, this complex undergoes decarbonylation to give the cluster [Os7(CO)19{Au2(dppx)}] (x=m (4), e (5), b (6)). The complexes have been characterised spectroscopically, and an X-ray structure determination of the dppm derivative shows that it contains a metal core based on an Os7 edge-bridged bicapped tetrahedron with the two
3-Au atoms capping adjacent triangular Os3 faces of the central tetrahedron. In an analogous reaction, the carbido anion [Os7(H)C(CO)19]– affords the neutral cluster [Os7C(CO)19{Au2(dppm)}] (7) when treated with [Au2(dppm)]2+ in the presence of base. 相似文献
25.
Ultraviolet irradiation (photolysis) in alkaline medium was applied for pretreatment of seawater samples so as to accurately determine total As by continuous-flow hydride generation-atomic fluorescence spectrometry. This sample pretreatment is meant to convert non-reducible As forms into inorganic As, which easily forms arsine. The optimised parameters were the treatment time and the pH of the medium. The behaviour of four hydride-reactive As species [As(III), As(V), MMA, DMA], and AsB, i.e. a typical non-hydride-reactive As species, when subjected to UV irradiation was studied. UV irradiation at pH 1 lead to conversion of all species into As(V) with the exception of AsB and DMA. Conversions of DMA and AsB into As(V) at pH 11 in less than 30 min were observed under UV irradiation. The limit of detection of As (measured as As(V)) by hydride generation-atomic fluorescence spectrometry was 0.1 μg/L and the repeatability of the oxidation procedure was about 10%. The method was applied to determination of total and directly reducible As at 11 sampling points of the Galician Coast (Atlantic Ocean, Spain). Total As concentrations were in the range 1.4-4.8 μg/L. A significant As fraction, between 20 and 44%, depending on the sampling point, corresponded to non-reducible As which was converted by UV irradiation into hydride-reactive As. This fraction should represent the sum of DMA, which yields a low sensitivity in the continuous flow-AFS system, and the hidden As fraction. 相似文献
26.
The Hill determinant method is shown to be suitable for constructing potential energy curves of diatomic molecules. Both the Dunham and the perturbed Morse oscillator potentials are used to fit spectroscopic data. Results are shown for ionic and covalent molecules. 相似文献
27.
Varietal compounds have been analyzed in wines prepared in the laboratory from four grape varieties grown in Spain. The possibilities for enhancing their aroma afforded by addition of glycosidase enzymes and steeping with the skin were studied. Both treatments increased substances responsible for varietal aroma in all wines, the effect being particularly significant for benzyl alcohol. 相似文献
28.
Liliana N. Trevani Jenene C. Roberts Peter R. Tremaine 《Journal of solution chemistry》2001,30(7):585-622
The spectra of copper(II)–ammonia solutions in 2 mol-kg–1 NH4NO3(aq) were recorded as a function of pH with a new UV–visible flow cell, capable of operating at conditions up to 325°C and 300 bars. Equilibrium constants for the formation of copper(II)–ammonia complexes Cu(NH3)n
2+, 1 n 4, from 30 to 150°C were determined by evolving factor analysis and nonlinear least-squares regression. Measurements at higher temperatures were limited by thermal decomposition of NH4NO3(aq). The formation constants of Cu(NH3)n
2+ decrease with temperature, consistent with extrapolations of literature data from measurements below 100°C. Measurements above 150°C were carried out in 0.5 mol-kg–1 CF3SO3H (aq), at the very high ammonia concentrations required to avoid the precipitation of CuO(s). The spectra are consistent with Cu(NH3)4
2+ as the predominant species, based on extrapolations of peak maxima and molar absorptivities from lower temperatures. Shifts in the spectra of Cu2+ and the Cu(NH3)n
2+ species to higher wavelength and increases in molar absorbance with increasing temperature are discussed in terms of the structure of the complexes. 相似文献
29.
Michel Spiesser Robert P. Gruska S.N. Subbarao Carlos A. Castro Aaron Wold 《Journal of solid state chemistry》1978,26(2):111-114
Crystals of antimony-doped In2Se3 were grown by the Bridgeman method. This compound, whose composition is In1.8Sb0.2Se3, appears to be isostructural with In1.9As0.1Se3. The refined unit cell parameters are a = 3.97(1), c = 18.87(1) Å. Orthorhombic crystals of InSbSe3 were grown from an isothermal melt. The refined unit cell parameters are a = 9.43(1), b = 14.02(5), and c = 3.96(1) Å. These parameters agree with those determined for α-InSbSe3 by other studies. The observed densities measured by a hydrostatic technique are 5.98(3) g/cm3 for In1.8Sb0.2Se3 and 6.07(2) g/cm3 for InSbSe3. The room temperature dc resistivity for In1.8Sb0.2Se3 has been found to be 4.4 × 104 Ω-cm, whereas that of InSbSe3 has been found to be 15.2(1) Ω-cm. A resistivity versus temperature study has beenn carried out for InSbSe3 between 230 and 400°K. Optical studies indicate that In1.8Sb0.2Se3 is an n-type semiconductor with a band gap of 1.1 eV and InSbSe3 is a p-type semiconductor with a band gap of 0.92 eV. 相似文献
30.
Guimarães KL Castro RH Gouvêa D 《Langmuir : the ACS journal of surfaces and colloids》2005,21(25):11645-11650
The standard methods for obtaining adsorption isotherms on colloidal suspensions are usually very time consuming and involve a large number of steps and assumptions that increase the experimental errors. In this work, an alternative method is proposed to evaluate the adsorption behavior of electrosteric-stabilized systems based on electrokinetic sonic amplitude signal measurements. The new method, entitled "zeta-sorption", is noticeably less time-consuming when compared to conventional procedures but showed great precision and reliability confirmed by comparison with data obtained from conventional routes on alumina-polyacrylate and alumina-citric acid aqueous suspensions. The experimental conditions that restrict the applicability of the new method were identified and justified by discussing the possible ion exchanges. 相似文献