全文获取类型
收费全文 | 195篇 |
免费 | 9篇 |
国内免费 | 3篇 |
专业分类
化学 | 132篇 |
晶体学 | 1篇 |
力学 | 6篇 |
数学 | 51篇 |
物理学 | 17篇 |
出版年
2023年 | 4篇 |
2021年 | 2篇 |
2020年 | 2篇 |
2019年 | 5篇 |
2018年 | 4篇 |
2017年 | 4篇 |
2016年 | 6篇 |
2015年 | 3篇 |
2014年 | 11篇 |
2013年 | 8篇 |
2012年 | 16篇 |
2011年 | 23篇 |
2010年 | 12篇 |
2009年 | 11篇 |
2008年 | 11篇 |
2007年 | 17篇 |
2006年 | 16篇 |
2005年 | 12篇 |
2004年 | 11篇 |
2003年 | 5篇 |
2002年 | 5篇 |
2001年 | 2篇 |
2000年 | 7篇 |
1999年 | 4篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 1篇 |
排序方式: 共有207条查询结果,搜索用时 15 毫秒
1.
Twelve-membered ring pseudopeptidic cyclic disulfides have been prepared by iodine oxidation of the parent dithiols. However, oxidation of N,N′-(1,2-phenylene)bis(2-mercapto-2-methylpropanamide) afforded a 25/75 mixture of cyclic mono- and bis-disulfides that were separated by selective precipitation in CHCl3. The cyclic bis-disulfide was selectively prepared by iodine oxidation of the Ni complex of this dithiol and crystallized. Its crystal structure was solved by X-ray diffraction. All these cyclic mono- or bis-disulfides were selectively converted to cyclic mono- and bis-thiosulfinates upon stoichiometric oxidation with dimethyldioxirane at low temperature. 1H NMR of the cyclic bis-thiosulfinate revealed the presence of four isomers, two couples of stereoisomers, as expected from the insertion of two oxygen atoms in this compound, one on each disulfide bond. The two couples of cis/trans isomers were separated by preparative TLC and identified after alkaline cleavage of the two S(O)-S bonds and metalation with Ni(II). As HO− attack is selective for the sulfinyl sulfur, the nature of the Ni complexes obtained is a signature of each couple of stereoisomers. 相似文献
2.
We consider a class of problems originating from a Raman laser amplification model, for which the equations can be written as a Poisson system with boundary conditions. Once reformulated, this system becomes an integro-differential equation that we study here in some detail. In particular, we show the existence of a smooth solution under general assumptions, and prove its uniqueness for boundary values that are not too far apart. Eventually, we completely solve the question of uniqueness for systems of dimensions one and two. To cite this article: F. Castella et al., C. R. Acad. Sci. Paris, Ser. I 336 (2003). 相似文献
3.
[reaction: see text] A stereoselective synthesis of (-)-ilimaquinone (4) is presented. The synthetic strategy is based on a novel radical decarboxylation and quinone addition methodology that produces quinone 7 from reaction of thiohydroxamic acid derivative 8 with benzoquinone (9). Final functionalization of 7 to ilimaquinone (4) is achieved by exploring the electronic effects of the residual thiopyridyl group. 相似文献
4.
Synthesis of methylenedioxy-bearing 1-aryl-3-carboxylisoquinolines using a modified Ritter reaction procedure 总被引:1,自引:0,他引:1
This paper describes original approaches aimed at the preparation of electron-rich 1-aryl-3-carboxylisoquinolines. Our first attempt led to an efficient preparation of 1-hydroxyisoquinoline-3-carboxylic acid methyl ester starting from bromophthalide via a rearrangement of 2-acetylamino-2-(3-oxo-1,3-dihydroisobenzofuran-1-yl)-malonic acid dimethyl ester. However, as its eventual application to the synthesis of methylenedioxy-bearing substrates seemed rather long, a second approach involving an extension of the Ritter reaction to safrole was devised. We thus report that, under proper experimental settings, the use of 54% tetrafluoroboric acid in ether enables a Ritter reaction between safrole and 3,4,5-trimethoxybenzonitrile yielding 17% of 7-methyl-5-(3,4,5-trimethoxyphenyl)-7,8-dihydro-[1,3]dioxolo[4,5-g]isoquinoline. This acidic reagent avoids the extensive decomposition seen when using the classical Ritter reaction conditions (i.e.: concentrated sulfuric acid). Further chemical transformations of this methyl-bearing dihydroisoquinoline led to the methylenedioxy-bearing 1-aryl-3-carboxylisoquinoline. These derivatives are related to the peripheral benzodiazepine receptor ligand PK 11195 as well as falcipain-2 inhibitors and other potential antitumor agents. 相似文献
5.
Mathieu Gaudin Maï Panchal Sophie Ayciriex Erwan Werner Alain Brunelle David Touboul Claire Boursier‐Neyret Nicolas Auzeil Bernard Walther Charles Duyckaerts Olivier Laprévote 《Journal of mass spectrometry : JMS》2014,49(10):1035-1042
The development of ‘omics’ sciences offers new opportunities for the study of neurodegenerative diseases but increases at the same time the sample demand on brain banks that collect and store valuable human post‐mortem tissue. Our study aims to evaluate in lipidomics the potential of formalin‐fixed tissue compared with the cryopreservation method, considered as the gold standard for biochemical research. Two complementary liquid chromatography/mass spectrometry analytical platforms were used on the basis of hybrid quadrupole time‐of‐flight and triple quadrupole mass spectrometers. Untargeted fingerprinting, semitargeted profiling of specific lipid classes and targeted monitoring of lipid species were performed in formalin‐fixed and cryopreserved samples to provide detailed information at the molecular level on the formalin‐induced alterations of the brain tissue. In vitro incubations of lipid standards were also performed to further describe the degradation processes induced by formaldehyde. Phospholipid compounds were found to be extensively hydrolysed, whilst the sphingolipid ones were preserved. N‐methylation and N‐formylation of amine‐containing phospholipids have also been evidenced. These findings show that the potential detrimental effect of formalin on the analytes of interest must be taken into account when analysing formalin‐fixed samples. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
6.
Dr. Marc Presset Dr. Jérôme Paul Ghania Nait Cherif Nisanthan Ratnam Nicolas Laloi Prof. Eric Léonel Dr. Corinne Gosmini Prof. Erwan Le Gall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(17):4491-4495
The reductive Barbier coupling of aromatic halides and electrophiles has been achieved using a CoBr2/1,10-phenanthroline catalytic system and over stoichiometric amounts of zinc. The reaction displayed a broad scope of substrates, including (hetero)aryl chlorides as pro-nucleophiles and aldehydes or imines as electrophiles, leading to diarylmethanols and diarylmethylamines in moderate to excellent yields, respectively. 相似文献
7.
We consider the Vlasov-HMF (Hamiltonian Mean-Field) model. We consider solutions starting in a small Sobolev neighborhood of a spatially homogeneous state satisfying a linearized stability criterion (Penrose criterion). We prove that these solutions exhibit a scattering behavior to a modified state, which implies a nonlinear Landau damping effect with polynomial rate of damping. 相似文献
8.
9.
We consider discretized Hamiltonian PDEs associated with a Hamiltonian function that can be split into a linear unbounded operator and a regular nonlinear part. We consider splitting methods associated with this decomposition. Using a finite-dimensional Birkhoff normal form result, we show the almost preservation of the actions of the numerical solution associated with the splitting method over arbitrary long time and for asymptotically large level of space approximation, provided the Sobolev norm of the initial data is small enough. This result holds under generic non-resonance conditions on the frequencies of the linear operator and on the step size. We apply these results to nonlinear Schrödinger equations as well as the nonlinear wave equation. 相似文献
10.
毛二万 《高校应用数学学报(英文版)》1999,14(4)
To some two-period economies with countable infinite state spaces,the existence of expectation equilibrium of real asset economies with transaction costs is given. This work extends the researches of Zame in 1993. 相似文献