全文获取类型
收费全文 | 3790篇 |
免费 | 317篇 |
国内免费 | 257篇 |
专业分类
化学 | 2482篇 |
晶体学 | 33篇 |
力学 | 109篇 |
综合类 | 6篇 |
数学 | 312篇 |
物理学 | 1422篇 |
出版年
2024年 | 7篇 |
2023年 | 113篇 |
2022年 | 34篇 |
2021年 | 27篇 |
2020年 | 63篇 |
2019年 | 74篇 |
2018年 | 72篇 |
2017年 | 69篇 |
2016年 | 88篇 |
2015年 | 78篇 |
2014年 | 122篇 |
2013年 | 305篇 |
2012年 | 266篇 |
2011年 | 168篇 |
2010年 | 148篇 |
2009年 | 213篇 |
2008年 | 259篇 |
2007年 | 237篇 |
2006年 | 205篇 |
2005年 | 212篇 |
2004年 | 204篇 |
2003年 | 152篇 |
2002年 | 129篇 |
2001年 | 111篇 |
2000年 | 112篇 |
1999年 | 92篇 |
1998年 | 104篇 |
1997年 | 70篇 |
1996年 | 63篇 |
1995年 | 55篇 |
1994年 | 66篇 |
1993年 | 44篇 |
1992年 | 58篇 |
1991年 | 42篇 |
1990年 | 35篇 |
1989年 | 25篇 |
1988年 | 34篇 |
1987年 | 30篇 |
1986年 | 26篇 |
1985年 | 15篇 |
1984年 | 18篇 |
1983年 | 6篇 |
1982年 | 16篇 |
1981年 | 17篇 |
1980年 | 21篇 |
1979年 | 19篇 |
1978年 | 7篇 |
1977年 | 11篇 |
1976年 | 8篇 |
1973年 | 6篇 |
排序方式: 共有4364条查询结果,搜索用时 15 毫秒
61.
The overall stability constantsK
1 andK
2 of NdNO
3
2+
and Nd(NO3)
2
+
complexes were determined (K
1=1.77;K
2=1.28) using an extraction method with tri-n-butyl phosphate as the extractant. The ratio 1/2 of the stepwise stability constants is discussed. It was established that the Nd(NO3)
2
+
complex was an outer-sphere ion pair.
Die Assoziation von Nitrat-Ion mit Nd3+
Zusammenfassung Mittels einer Extraktionsmethode wurden die StabilitätskonstantenK 1 undK 2 von NdNO 3 2+ - und Nd(NO3)+-Komplexen bestimmt (K 1=1.77;K 2=1.28; Tri-n-butylphosphat als Extraktionsmittel). Das Verhältnis 1/2 der stufenweisen Stabilitätskonstanten wird diskutiert. Es stellte sich heraus, daß der Nd(NO3)+-Komplex als ein Outer-Shere-Ionenpaar vorliegt.相似文献
62.
The molar conductances of dilute solutions of salicylic and monochloroacetic acids in binary mixtures of methanol, ethanol, 1-propanol, N,N-dimethylformamide, acetone, acetonitrile, tetrahydrofuran and dioxane with water have been measured at 25°C. The Lee-Wheaton conductance equation was fitted to the data in order to derive thermodynamic dissociation constants and limiting molar conductances. The results were compared with those in the literature pertaining to analogous media, mostly derived potentiometrically. The findings are interpreted in terms of a solvent effect on the ionization of these acids in mixed solvent systems.This paper is dedicated to the late Professor Raymond M. Fuoss on his 3rd anniversary. 相似文献
63.
Absolute rate constants are reported for the addition of the 1‐[(tert‐butoxy)carbonyl]ethyl (= 2‐(1,1‐dimethylethoxy)‐1‐methyl‐2‐oxoethyl) radical .CHMeCO2(t‐Bu) to several cyclic and monosubstituted alkenes in MeCN as obtained by time‐resolved electron paramagnetic resonance (EPR). The activation energies for the addition of this alkyl radical are mainly governed by the addition enthalpy but are also substantially lowered by the ambiphilic effect and by relief of cyclic strain. 相似文献
64.
Solubilities are reported for carbazole in three binary chloroalkane + dibutyl ether solvent mixtures at 25°C. Results of these measurements are compared with solution models developed for solubility in systems containing specific solute-solvent interactions. A simple model based on a single 1:1 carbazole:dibutyl ether complex described the solubility data, though the calculated equilibrium constant was about one-half of values published previously. A more sophisticated solution model, which assumes both carbazole:dibutyl ether and carbazole:chloroalkane complexes, was needed to thermodynamically describe the systems studied. Equilibrium constants for three presumed carbazole:chloroalkane complexes are calculated from measured carbazole solubilities. 相似文献
65.
New spin-state-selective (S3) NMR pulse sequences exclusively applying cross-polarization schemes to achieve optimum homonuclear and heteronuclear 1H-X coherence transfer are reported for the simple and accurate measurement of the magnitude and sign of heteronuclear coupling constants for samples at natural abundance. The proposed spin-edited HCP-TOCSY experiments are based on clean heteronuclear S3 excitation, generated by simultaneous co-addition of two independent in-phase and anti-phase components created during the mixing heteronuclear J-cross-polarization (HCP) step, which is finally transferred to other protons by a conventional homonuclear TOCSY mechanism. Selective 1D and non-selective 2D approaches for the easy determination of long-range proton-carbon and proton-nitrogen coupling constants on any protonated and non-protonated heteronuclei are presented and discussed for several organic molecules. 相似文献
66.
Terenina M. B. Misharina T. A. Krikunova N. I. Golovnya R. V. 《Russian Chemical Bulletin》2001,50(6):1032-1036
Capillary gas chromatography was applied to study the sorption of aliphatic ketones (C6—C11), including metamers, from aqueous solutions by corn starch cryotextures. The amount of ketones sorbed by cryotextures depends linearly on their concentrations in the initial sol. Equations describing the concentration dependence of sorption were proposed. The shape of sorption isotherms reflects the strength of sorption. The binding constants and the number of binding sites were determined for weakly sorbed ketones. The length of alkyl substituent and the position of the functional group are the crucial factors governing the sorption of ketones under conditions of excess binding sites. It was found that the degree of sorption increases with an increase in the carbon chain length from 6 to 9 carbon atoms. The presence of cooperation of binding sites for ketone sorption by cryotextures was demonstrated. The major part of ketones is sorbed irreversibly. This fact points to the formation of supramolecular complexes. Ketones with lower molecular masses are better sorbed by cryotextures than by native starch grains. 相似文献
67.
Eckhard Herrmann Moein Nouaman Zdirad
k Gisbert Großmann Gisela Ohms 《无机化学与普通化学杂志》1994,620(11):1879-1888
Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by 1H, 13C, and 31P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the 2JP? N? P coupling constants were determined by 13C{1H, 31P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group. 相似文献
68.
Summary The interaction of some benzene and naphthalene derivatives with sodium dodecyl sulphate, hexadecyltrimethylmmonium bromide and polyoxyethylene [23] dodecanol micelles has been evaluated by high operformance liquid chromatography using micellar mobile phases. The micelle-solute association constants have been obtained for the compounds investigated. Good correlation between free energy of transfer for water-micelles and for octanol-water has been observed. 相似文献
69.
Summary The basic dissociation constants for a series of 30 4-aminopyrimidine and 2,4-diaminopyrimidine derivatives were determined in 2% v/v aqueous methanol by a spectrophotometric method. The determinedpK
a values correlate well withHammet's constants.
Basizität von 4-Aminopyrimidin- und 2,4-Diaminopyrimidinderivaten
Zusammenfassung Die basischen Dissoziationskonstanten einer Reihe von 30 4-Aminopyrimidin-and 2,4-Diaminopyrimidinderivaten wurden in 2% v/v wäßrigem Methanol durch spektroskopische Methoden bestimmt. Die ermitteltenpK a-Werte korrelieren gut mit den entsprechendenHammett-Parametern .相似文献
70.
The formation constants of the mono-adducts of α-acylcamphorato-copper(II) chelates such as (+)-Cu(facam)2, (?)-Cu(facam)2, (+)-Cu(hfbc)2 and (?)-Cu(hfbc)2 with some chiral Lewis bases were determined spectrophotometrically in benzene. In order to compare the adduct formation constants obtained with the (+)- and (?)-forms, some pairs of chiral Lewis bases such as 1-amino-2-propanol [(R)(?), (S)(+)], 1-(α-naphthyl)ethylamine [(R)(+), (S)(?)], α-phenyl ethylamine [(R)(+), (S)(?)] and also quinine and quinidine were examined as neutral ligands. Although not very pronounced, the effects of combinations obtained for (+)- or (?)-Cu(II) chelates and (+)- or (?)-ligands indicate that formation constants obtained by the formation of adducts with the ligands having different directions of the optical rotation seems to be superior to those with the same direction. 相似文献