全文获取类型
收费全文 | 394篇 |
免费 | 3篇 |
专业分类
化学 | 240篇 |
力学 | 30篇 |
数学 | 77篇 |
物理学 | 50篇 |
出版年
2022年 | 4篇 |
2021年 | 7篇 |
2020年 | 3篇 |
2019年 | 4篇 |
2017年 | 5篇 |
2016年 | 11篇 |
2015年 | 12篇 |
2014年 | 9篇 |
2013年 | 28篇 |
2012年 | 19篇 |
2011年 | 22篇 |
2010年 | 19篇 |
2009年 | 6篇 |
2008年 | 12篇 |
2007年 | 16篇 |
2006年 | 18篇 |
2005年 | 14篇 |
2004年 | 14篇 |
2003年 | 11篇 |
2002年 | 16篇 |
2001年 | 6篇 |
2000年 | 6篇 |
1998年 | 8篇 |
1997年 | 6篇 |
1996年 | 2篇 |
1995年 | 5篇 |
1994年 | 4篇 |
1993年 | 7篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1989年 | 8篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 5篇 |
1984年 | 6篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1978年 | 6篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1942年 | 2篇 |
1940年 | 3篇 |
1891年 | 3篇 |
排序方式: 共有397条查询结果,搜索用时 31 毫秒
11.
Mario Bianchi Ugo Matteoli Piero Frediani Gloria Menchi Franco Piacenti 《Journal of organometallic chemistry》1982,236(3):375-380
Hydrogen transfer from racemic alcohols to prochiral ketones in the presence of H4Ru4(CO)8[(?)-DIOP]2 has been examined. The enantiomer-discrimination is influenced by the structure of the reactants, temperature and the excess of phosphine present. 相似文献
12.
Ugo Caruso Antonella De Maria Barbara Panunzi Antonio Roviello 《Journal of polymer science. Part A, Polymer chemistry》2002,40(17):2987-2993
Two formulas of grafted polymers with metal‐containing chromophores, potentially suitable for second‐order nonlinear optics applications, are described. Two chromophores were obtained from a tridentate ligand coordinated to Cu(II) or Pd(II) ions. The organometallic chromophore fragments were grafted to poly(4‐vinylpyridine) by the pyridinic nitrogen of the host polymer. Some qualities displayed by the new metallated polymers are remarkable: (1) a high value of the first hyperpolarizability coefficient of the chromophores, (2) a high content of the grafted chromophore in the polymers (up to 60 wt %), (3) a considerable increase in the glass‐transition temperatures (up to 240 °C), (4) good thermal stability in air (ca. 280 °C), and (5) good optical transparency of the films. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2987–2993, 2002 相似文献
13.
Giampiero Bartocci Anna Spalletti Ugo Mazzucato 《Research on Chemical Intermediates》1995,21(7):735-747
A fluorimetric and photochemical study of cis-9-styrylanthracene as a function of temperature has been carried out in different solvents with the aim of answering some open questions about the behavior of its first excited singlet state, S1. In non-polar solvents, a parallel photoreactive pathway, leading to a cyclization adduct, was found to compete with fluorescence and isomerization already at 200 K, its contribution increasing markedly with temperature. The cis » trans photoisomerization occurs prevalently by a triplet mechanism, a detectable contribution of diabatic and adiabatic isomerization in S1 being operative in these solvents from room temperature upwards. In polar solvents, the main deactivation pathway competitive with fluorescence is isomerization to trans, which occurs prevalently through a mixed singlet mechanism with a major diabatic and a minor adiabatic components. 相似文献
14.
In a recent paper we have solved several well-known combinatorial problems treating them as special cases of our generalization of Shannon's notion of graph capacity. We present a new simple formalism to deal with all such problems in a unified manner, considering graphs or families of graphs as special formulæ the variables of which are pairs of vertices of their common vertex sets. In all of these problems, the maximum size of a set ofn-length sequences from a fixed alphabet is to be determined under various restrictions on the element pairs present in the same coordinate of any two sequences from the set. For sufficiently homogeneous formulæ capacity becomes computable.New applications include generalizations of our result on the maximum number of pairwise qualitatively independentk-partitions of ann-set from independence to various forms of qualitative dependence.Work partially supported by the Italian Ministry of the University and Scientific Research, Project: Algoritmi, Modelli di Calcolo e Strutture Informative. 相似文献
15.
Ortica F Moustrou C Berthet J Favaro G Samat A Guglielmetti R Vermeersch G Mazzucato U 《Photochemistry and photobiology》2003,78(6):558-566
A photophysical and photochemical study of a biphotochromic compound where two naphthopyran units are linked by an acetylene-thiophene-acetylene bridge has been carried out in toluene. Both fluorescence and intersystem crossing to the triplet manifold were found to compete with the photocoloration process. Two photoproducts (transoid-trans and transoid-cis stereoisomers), absorbing at approximately 480 nm and corresponding to the opening of a single photochromic unit, were detected by spectrophotometric analysis after short irradiation time in diluted solution and identified by 1H-nuclear magnetic resonance (NMR) spectroscopy. After prolonged irradiation at 228 K of highly concentrated solutions (up to 3 x 10(-3) mol dm(-3)), two additional isomers, absorbing at approximately 550 nm, were formed. Their NMR spectra indicate the opening of both photochromic units. An interesting effect of selective vibronic excitation was found, showing that the photoreaction is favored at excited vibronic levels to the detriment of the radiative relaxation. 相似文献
16.
Pedro Merino Julia RevueltaTomas Tejero Ugo ChiacchioAntonio Rescifina Giovanni Romeo 《Tetrahedron》2003,59(20):3581-3592
In the 1,3-dipolar cycloaddition of glyoxylic nitrones with electron-poor and electron-rich alkenes, the configurational instability of the nitrone leads to parallel models when regio- and stereoselectivities are rationalized. The energetics of the cycloaddition reactions have been investigated through molecular orbital calculations at the B3LYP/6-31-G(d) theory level. By studying different reaction channels and reagent conformations, leading to a total of sixteen transition structures for each dipolarophile, the regio- and stereochemical preferences of the reaction are discussed. 相似文献
17.
The electroanalytical method described for the simultaneous determination of concentration, the number of electrons involved in the redox process and diffusion coefficient is based on evaluation of the ratios between the currents recorded for the analyte and for an easily standardized reference species dissolved in the same medium. Three different electroanalytical techniques are used in which the currents exhibit, for two techniques at least, different dependences on both the diffusion coefficient and electron number. The approach is applicable to diffusion-controlled processes, regardless of the degree of reversibility involved. Reliability tests with electroactive organic compounds dissolved in dimethyl sulphoxide show that both accuracy and precision are within 10% depending on the chosen combination of techniques. 相似文献
18.
2-and 4-Ethoxymethoxybenzyl methyl ethers were employied as useful starting materials for the synthesis of 1,2- or 1,4-dicarbo-substituted benzenes. The proposed reaction sequence involves connection between the reductive lithiation of benzyl alkyl ethers and the metal-catalyzed cross-coupling reaction of aromatic triflates. 相似文献
19.
Salvatore Daniele Maria-Antonietta Baldo Paolo Ugo Gian-Antonio Mazzocchin 《Analytica chimica acta》1989
Differential-pulse anodic stripping voltammetry with a mercury microelectrode is used for the determination of zinc, cadmium, lead and copper in wine at its natural pH without pretreatment. The effects of the matrix on the stripping peaks are studied in detail by varying the concentration of the metals. Intermetallic (CuZn) interferences and the effects of oxygen are described. The results obtained for the labile metal contents varied from 2 μg l?1 for cadmium to 148 μg l?1 for zinc; standard addition plots were linear over about two orders of magnitude above these levels, demonstrating the negligible effect of organic matter. Acidification of the sample with hydrochloric acid to pH 1 allowed the total metal contents to be determined. The reliability of the method was tested by comparison with the results obtained with atomic absorption spectrometry; the differences were within 10–20%. 相似文献
20.
Haplotype studies support slippage as the mechanism of germline mutations in short tandem repeats 总被引:1,自引:0,他引:1
Klintschar M Dauber EM Ricci U Cerri N Immel UD Kleiber M Mayr WR 《Electrophoresis》2004,25(20):3344-3348
Germline mutations of human short tandem repeat (STR) loci are expansions or contractions of repeat arrays which are not well understood in terms of the mechanism(s) underlying such mutations. Although polymerase slippage is generally accepted as a mechanism capable to explain most features of such mutations, it is still possible that unequal crossing over plays some role in those events, as most studies in humans could not exclude unequal crossing over (UCO). Crossing over can be studied by analyzing haplotypes using flanking markers. To check for UCO in mutations, we have analyzed 150 paternity cases for which more than the usual trio (mother, child, and father) were available for testing by analyzing 16 STR loci. In a total of 4900 parent-child allele transfers four mutations were observed at different loci (D8S1179, D18S51, D21S11, and SE33/ACTBP2). To identify the mutated allele and to check for UCO, we typed at least four informative loci flanking the mutated locus and used the pedigree data to establish haplotypes. By doing so we were able to exclude UCO in each case. Moreover, we were able to identify the mutations as one-repeat contractions/expansions. Our data thus support slippage as the mechanism of germline mutations in STRs. 相似文献