全文获取类型
收费全文 | 768篇 |
免费 | 0篇 |
国内免费 | 16篇 |
专业分类
化学 | 469篇 |
晶体学 | 2篇 |
力学 | 35篇 |
数学 | 139篇 |
物理学 | 139篇 |
出版年
2023年 | 2篇 |
2022年 | 11篇 |
2021年 | 12篇 |
2020年 | 6篇 |
2019年 | 8篇 |
2018年 | 11篇 |
2017年 | 7篇 |
2016年 | 11篇 |
2015年 | 9篇 |
2014年 | 20篇 |
2013年 | 47篇 |
2012年 | 45篇 |
2011年 | 54篇 |
2010年 | 34篇 |
2009年 | 27篇 |
2008年 | 47篇 |
2007年 | 57篇 |
2006年 | 49篇 |
2005年 | 39篇 |
2004年 | 53篇 |
2003年 | 36篇 |
2002年 | 30篇 |
2001年 | 10篇 |
2000年 | 8篇 |
1999年 | 7篇 |
1998年 | 8篇 |
1997年 | 15篇 |
1996年 | 6篇 |
1995年 | 12篇 |
1994年 | 10篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 8篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 7篇 |
1982年 | 11篇 |
1981年 | 5篇 |
1980年 | 6篇 |
1978年 | 5篇 |
1977年 | 2篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有784条查询结果,搜索用时 15 毫秒
1.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
2.
Jean-Marc Hérard 《Comptes Rendus Mathematique》2006,342(10):779-784
We introduce a hyperbolic entropy-consistent model to describe three-phase flows, which ensures that void fractions, mass fractions and pressures remain positive through single waves occurring in the one dimensional solution of the Riemann problem. To cite this article: J.-M. Hérard, C. R. Acad. Sci. Paris, Ser. I 342 (2006). 相似文献
3.
Aza-Michael addition of optically pure 4-phenyl-2-oxazolidinone to 3,3,3-trifluoro-1-nitropropene proceeds smoothly at low temperature with a high yield. Diastereoselectivity of the addition depends on the base used and lithiated species proved to be highly efficient affording 92% de. Optically pure 1,2-diamino-3,3,3-trifluoropropane is prepared in 58% yield from the aza-Michael addition product through a three-step procedure. 相似文献
4.
5.
Frédéric Coquel Thierry Gallouët Jean-Marc Hérard Nicolas Seguin 《Comptes Rendus Mathematique》2002,334(10):927-932
Closure laws for interfacial pressure and interfacial velocity are proposed within the frame work of two-pressure two-phase flow models. These enable us to ensure positivity of void fractions, mass fractions and internal energies when investigating field by field waves in the Riemann problem. To cite this article: F. Coquel et al., C. R. Acad. Sci. Paris, Ser. I 334 (2002) 927–932. 相似文献
6.
Valérie Michaut Jean-Marc Paris Jean-Christophe Plaquevent 《Journal of fluorine chemistry》2007,128(8):889-895
Herein are studied new transformations of ethyl-4,4,4-trifluoroacetoacetate (ETFAA), giving access to a series of enantiopure chirons bearing both a trifluoromethyl group and an amino moiety. The key intermediate is obtained optically pure by a resolution procedure. 相似文献
7.
Jean-Marc Kern Jean-Pierre Sauvage Gerard Bidan Bernadette Divisia-Blohorn 《Journal of polymer science. Part A, Polymer chemistry》2003,41(22):3470-3477
This article provides an overview of the fundamental principles of the synthesis of metallocatenanes and metallorotaxanes. It also describes the synthesis and properties of electronic conducting polymers—polypyrrole and polythiophene—built around metallocatenanes and metallorotaxanes. The particular properties of this new class of polymers, including the possibility of transmetallation reactions being performed with them and the observation of electronic coupling between the metal centers and the conducting matrix, are discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3470–3477, 2003 相似文献
8.
Eleonora Catsigeras Jean-Marc Gambaudo Fernando Moreira 《Proceedings of the American Mathematical Society》1998,126(1):297-304
We show that, among area contracting embeddings of the 2-disk, infinitely renormalizable maps with a bounded geometry either have positive topological entropy or correspond to a cascade of period doubling.
9.
Berquier Jean-Marc Nael Pascal Jupille Jacques Jacquiod Catherine 《Journal of Sol-Gel Science and Technology》2000,19(1-3):83-87
Fourier Transform Infrared transmission spectroscopy is used to characterize surfactant-templated silica films on glass. The calcination process is followed in situ and evidence for the removal of the surfactant along the Hoffman reaction is given. Once calcined, the surface of the pores of the mesoporous films is proven by deuteration experiment to be hydroxylated. Bands are attributed to isolated and hydrogen-bonded silanols. Silylation reaction with hexamethyldisilazane only occurs with isolated silanol groups. 相似文献
10.
Pd(dba)2[dba = dibenzylideneacetone]/PPh3-or Pd(PPh3)4-catalyzed cyclizations of acetoxy-dienes 2 → 3 and 10 → 11 gave 1-vinyl-2-methylidene-subsituted cyclopentances and cyclohexanes in high yield, consistent with a palladium-ene/β-elimination mechanism ( D → E → F , Scheme 2). The efficient and highly stereoselective cyclizations 7 → 7 and 8 → 9 illustrate intramolecular allylpalladium insertions into 1,2-dialkyl-, trialkyl-, trialkyl-, and cyclic alkenes followed by elimination of the exocyclic β–H giving 1,2-divinylcyclopentanes. These new olefin insertions proceed faster in AcOH (compared to THF) and occur preferentially cis relative to the Pd ( 13 → 14 → 15 ). 相似文献