全文获取类型
收费全文 | 1150篇 |
免费 | 19篇 |
国内免费 | 4篇 |
专业分类
化学 | 871篇 |
晶体学 | 13篇 |
力学 | 14篇 |
数学 | 109篇 |
物理学 | 166篇 |
出版年
2022年 | 6篇 |
2021年 | 12篇 |
2020年 | 15篇 |
2019年 | 14篇 |
2017年 | 6篇 |
2016年 | 23篇 |
2015年 | 23篇 |
2014年 | 21篇 |
2013年 | 60篇 |
2012年 | 55篇 |
2011年 | 74篇 |
2010年 | 49篇 |
2009年 | 43篇 |
2008年 | 58篇 |
2007年 | 58篇 |
2006年 | 43篇 |
2005年 | 48篇 |
2004年 | 46篇 |
2003年 | 36篇 |
2002年 | 40篇 |
2001年 | 17篇 |
2000年 | 16篇 |
1999年 | 17篇 |
1998年 | 15篇 |
1997年 | 12篇 |
1996年 | 13篇 |
1995年 | 10篇 |
1994年 | 10篇 |
1993年 | 13篇 |
1992年 | 11篇 |
1991年 | 8篇 |
1990年 | 18篇 |
1989年 | 9篇 |
1988年 | 13篇 |
1987年 | 12篇 |
1986年 | 15篇 |
1985年 | 19篇 |
1984年 | 20篇 |
1983年 | 11篇 |
1982年 | 23篇 |
1981年 | 11篇 |
1980年 | 18篇 |
1979年 | 19篇 |
1978年 | 11篇 |
1977年 | 10篇 |
1976年 | 10篇 |
1975年 | 6篇 |
1974年 | 7篇 |
1973年 | 11篇 |
1968年 | 5篇 |
排序方式: 共有1173条查询结果,搜索用时 31 毫秒
11.
Denis Prat Françoise Benedetti Lahlou Nait Bouda Gilles Franc Girard 《Tetrahedron letters》2004,45(4):765-768
An industrial synthesis of 11β-aryl-estrone derivatives is described, based on the 1,4-addition of the aryl side-chain, as a cuprate, on to a mixture of allylic 5(10) alpha and beta epoxides, followed by hydrolysis and subsequent aromatization. 相似文献
12.
Transverse displacement at total reflection near the grazing angle: a way to discriminate between theories 总被引:1,自引:0,他引:1
F. Pillon H. Gilles S. Girard M. Laroche O. Emile 《Applied physics. B, Lasers and optics》2005,80(3):355-357
The transverse shift is observed and precisely measured at total internal reflection on a dielectric interface for a circularly polarized light beam when the incident angle is scanned from the critical angle up to the grazing angle close to 90°. The experimental results show with no doubt that the transverse displacement exists far away from the critical angle and only vanishes at grazing angle. A comparison with theories also allows a discrimination between the most different theoretical models traditionally used to interpret physically this effect. 相似文献
13.
A. Girard 《Numerische Mathematik》1989,56(1):1-23
Summary We propose a fast Monte-Carlo algorithm for calculating reliable estimates of the trace of the influence matrixA
involved in regularization of linear equations or data smoothing problems, where is the regularization or smoothing parameter. This general algorithm is simply as follows: i) generaten pseudo-random valuesw
1, ...,w
n
, from the standard normal distribution (wheren is the number of data points) and letw=(w
1, ...,w
n
)
T
, ii) compute the residual vectorw–A
w, iii) take the normalized inner-product (w
T
(w–A
w))/(w
T
w) as an approximation to (1/n)tr(I–A
). We show, both by theoretical bounds and by numerical simulations on some typical problems, that the expected relative precision of these estimates is very good whenn is large enough, and that they can be used in practice for the minimization with respect to of the well known Generalized Cross-Validation (GCV) function. This permits the use of the GCV method for choosing in any particular large-scale application, with only a similar amount of work as the standard residual method. Numerical applications of this procedure to optimal spline smoothing in one or two dimensions show its efficiency. 相似文献
14.
Dupieux P Alard JP Augerat J Babinet R Bastid N Brochard F Charmensat P De Marco N Fanet H Fodor Z Fraysse L Girard J Gorodetzky P Gosset J Laspalles C Lemaire MC L'Hôte D Lucas B Marroncle J Montarou G Parizet MJ Poitou J Qassoud D Racca C Schimmerling W 《Physics letters. [Part B]》1988,200(1-2):17-21
Proton-proton small angle correlations have been measured in neon-nucleus collisions, using the 4 pi detector Diogene, at 400 and 800 MeV per nucleon incident energies. Values of the size of the emitting region are obtained by comparison with the Koonin formula, taking into account the biases of the apparatus. The dependence of the density on target mass and incident energy is also analysed. 相似文献
15.
Vladimir Rapić Prof. Dr. Karl Schlögl Brigitte Steinitz 《Monatshefte für Chemie / Chemical Monthly》1977,108(4):767-780
Starting from optically active methylferrocene-- and--carboxylic acids (1 a and1 b) of known absolute configuration and enantiomeric purity about 15 chiral ferrocenes (of each isomeric series— and ) were obtained by suitable ligand transformations. Thereby (almost) all possible chiral combinations of the ligands CH3, COOH (COO–), COOCH3, CN and NH2 (NH3
+) were accessible which are necessary for a potential test of approximations of chirality functions for compounds with basic symmetry C5v. The chiroptical properties of these disubstituted ferrocenes are recorded.Preliminary tests using a shortened Ansatz revealed large discrepancies between calculated () and found [M]D-values. Possible reasons for this failure are discussed.
61. Mitt. über Ferrocenderivate
39. Mitt.:A. Meyer, H. Neudeck undK. Schlögl, Chem. Ber.110, 1403 (1977).
60. Mitt.:V. Rapi, K. Schlögl undB. Steinitz, J. Organometal. Chem.94, 87 (1975). 相似文献
61. Mitt. über Ferrocenderivate
39. Mitt.:A. Meyer, H. Neudeck undK. Schlögl, Chem. Ber.110, 1403 (1977).
60. Mitt.:V. Rapi, K. Schlögl undB. Steinitz, J. Organometal. Chem.94, 87 (1975). 相似文献
16.
Jocelyn Jalbert Roland Gilbert Pierre Tétreault Brigitte Morin Denise Lessard-Déziel 《Cellulose (London, England)》2007,14(4):295-309
In this study, headspace gas chromatography/mass spectrometry has been used to assess the volatile by-products generated by
the ageing of oil-impregnated paper insulation of power transformers. Sealed-glass ampoules were used to age under oxidative
conditions 0.5-g specimens of insulating paper in 9 mL of inhibited mineral oil in a temperature range of 60–120 °C and moisture
of 0.5, 1 and 2% (w/w). A linear relationship between one of the oil-soluble degradation by-products, i.e. methanol, and the
number of ruptured 1,4-β-glycosidic bonds of cellulose, regardless of the type of paper (ordinary Kraft or thermally-upgraded
(TU) Kraft paper), was established for the first time in this field. Ageing at 130 °C of model compounds of the Kraft paper
constituents (α-cellulose, hemicellulose and lignin) and two cellulosic breakdown by-products (D-(+)-glucose and 1,6-anhydro-β-d-glucopyranose) confirmed that the α-cellulose degradation was mostly responsible for the presence of this molecule in the
system. Furthermore, additional 130 °C-tests with six different papers and pressboard samples under a tight control of initial
moisture indicated that at least one molecule of methanol is formed for each rupture of 1,4-β-glucosidic bond of the molecular
chains. Stability tests showed that the ageing indicator is stable under the oxygen and temperature conditions of open-breathing
transformers. The presence of methanol was detected in 94% of oil samples collected from over than 900 in-service pieces of
equipment, confirming the potential for this application. Lastly, the tests have shown that oil-oxidation by-products and
TU-nitrogenous agents modify the methanol partitioning coefficients in the paper/oil/air system, which makes their study essential
over a range of field conditions encountered by power transformers. Results are presented and discussed in comparison with
2-furfuraldehyde, which is the current reference in the domain. 相似文献
17.
Gerhard Buchbauer Waltraud Pernold Dorothea Rassl Brigitte Blach 《Monatshefte für Chemie / Chemical Monthly》1981,112(4):517-527
The synthesis of some new potentially, nitrogenefree spasmolytics is described. Formally the benzene nucleus in some mandelic acid esters, known by their mild spasmolytic activity, is substituted for the isocamphane bicyclus by a) SeO2 oxidation of 1-(3,3-Dimethyl-2-exo-norbornyl)-ethanone (5) to the corresponding ketoaldehyde6, b) oxidation of6 to the isocamphane analogous mandelic acid4 and c) esterification of derivatives of4 with isoamylalcohol and benzylalcohol. Attemps to dehydrate the methylester7 to camphenylideneacetic acid methylester (12) by various methods failed, probably because of the ring strain.
Teil der Diplomarbeit vonB. Blach, Universität Wien 1981. 相似文献
18.
Mono- or 1,1′-bis-acylation of ferrocene, its mono and 1,1′-dimethyl and phenyl derivatives and of [3]ferrocenophane with o-chlorobenzoyl chloride/AlCl3 affords the corresponding (isomeric) chlorobenzoyl ferrocenes in high yields which can be separated by column, layer or high pressure liquid chromatography and in the case of the monomethylferrocene monoketones also by crystallization. The cleavage of the (o-chlorobenzoyl)ferrocenes by potassium-t-butoxide (and traces of water) yields the corresponding ferrocene carboxylic acids except for the α-phenyl derivatives in almost quantitative yields, thus offering a very convenient access to these acids. In all cases the isomer distribution and thereby the relative site reactivities were determined. 相似文献
19.
The In-flame detector earlier applied to the specific chlorine (359.9 nm) and bromine (372.7 nm) analysis has now been employed for the iodine determination at 409.9 nm. It is shown that the resolution power of a GC column can be improved by such a specific detector. After calibration quantitative measurements of the iodine contents of the GC fractions are possible. The detection limits are 0.01–1.4 μg of iodine. 相似文献
20.
Gilbert Dana Feiga Weisbuch Brigitte Lo Cicero Jean-Michel Drancourt Jacqueline Mercier 《Tetrahedron》1985,41(7):1241-1249
We show that the four studied 4-hydrindenones (with or without a methyl substituant at C3 or C7a) give by hydrogenation on Raney nickel or on Pd/C, in various solvants, the cis 4-hydrindanones, by a kinetically controlled process. During the hydrogenation, the double bond can migrate only in the positions conjugated to the carbonyl group.In contrast, when the carbonyle is protected as a dioxolanne, the double bond is free to migrate around the five membered ring. In spite of this mobility the optical purity of the saturated dioxolannes formed is high. In the case of the (+)3-methyl Δ3(3a) 4-hydrindenone, the enantiomeric hydrindanones obtained by direct hydrogenation or with isomerization of the double bond are not the same. Therefore, the optical purity of the product is low, but its value allows an estimation of the relative importance of the two reaction pathways. 相似文献