全文获取类型
收费全文 | 935篇 |
免费 | 8篇 |
国内免费 | 16篇 |
专业分类
化学 | 567篇 |
晶体学 | 4篇 |
力学 | 40篇 |
数学 | 163篇 |
物理学 | 185篇 |
出版年
2023年 | 4篇 |
2022年 | 5篇 |
2021年 | 13篇 |
2020年 | 10篇 |
2019年 | 10篇 |
2018年 | 16篇 |
2017年 | 11篇 |
2016年 | 17篇 |
2015年 | 14篇 |
2014年 | 24篇 |
2013年 | 63篇 |
2012年 | 54篇 |
2011年 | 63篇 |
2010年 | 42篇 |
2009年 | 33篇 |
2008年 | 59篇 |
2007年 | 64篇 |
2006年 | 59篇 |
2005年 | 46篇 |
2004年 | 57篇 |
2003年 | 40篇 |
2002年 | 34篇 |
2001年 | 15篇 |
2000年 | 13篇 |
1999年 | 6篇 |
1998年 | 7篇 |
1997年 | 15篇 |
1996年 | 7篇 |
1995年 | 12篇 |
1994年 | 15篇 |
1993年 | 10篇 |
1992年 | 4篇 |
1991年 | 9篇 |
1989年 | 5篇 |
1986年 | 2篇 |
1985年 | 10篇 |
1984年 | 6篇 |
1983年 | 7篇 |
1982年 | 12篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 4篇 |
1978年 | 7篇 |
1977年 | 2篇 |
1976年 | 7篇 |
1975年 | 8篇 |
1974年 | 4篇 |
1973年 | 6篇 |
1971年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有959条查询结果,搜索用时 31 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.
3.
4.
The purpose of this paper is to construct a new non-parametric detector of univariate outliers and to study its asymptotic properties. This detector is based on a Hill’s type statistic. It satisfies a unique asymptotic behavior for a large set of probability distributions with positive unbounded support (for instance: for the absolute value of Gaussian, Gamma, Weibull, Student or regular variations distributions). We have illustrated our results by numerical simulations which show the accuracy of this detector with respect to other usual univariate outlier detectors (Tukey, MAD or Local Outlier Factor detectors). The detection of outliers in a database providing the prices of used cars is also proposed as an application to real-life database. 相似文献
5.
Jacinthe Frangieh Mohamad Rima Ziad Fajloun Daniel Henrion Jean-Marc Sabatier Christian Legros Csar Mattei 《Molecules (Basel, Switzerland)》2021,26(8)
Cardiovascular diseases (CVDs) are considered as a major cause of death worldwide. Therefore, identifying and developing therapeutic strategies to treat and reduce the prevalence of CVDs is a major medical challenge. Several drugs used for the treatment of CVDs, such as captopril, emerged from natural products, namely snake venoms. These venoms are complex mixtures of bioactive molecules, which, among other physiological networks, target the cardiovascular system, leading to them being considered in the development and design of new drugs. In this review, we describe some snake venom molecules targeting the cardiovascular system such as phospholipase A2 (PLA2), natriuretic peptides (NPs), bradykinin-potentiating peptides (BPPs), cysteine-rich secretory proteins (CRISPs), disintegrins, fibrinolytic enzymes, and three-finger toxins (3FTXs). In addition, their molecular targets, and mechanisms of action—vasorelaxation, inhibition of platelet aggregation, cardioprotective activities—are discussed. The dissection of their biological effects at the molecular scale give insights for the development of future snake venom-derived drugs. 相似文献
6.
Daniel Desbordes Henri Noël Presles Franckie Joubert Cresus Gbagdo Douala 《Comptes Rendus Mecanique》2004,332(12):993-999
Calculations of the detonation reaction zone of gaseous H2NO2/N2O4 mixtures in the range of equivalence ratio Φ between 0.25 and 0.7 show that for 0.25Φ0.4 the chemical energy is released in two distinct and successive exothermic steps characterised by different chemical characteristic times. As for rich mixtures, the first exothermic step is mainly due to the reaction NO2 + H → NO + OH, but the second one is different since it results from the exothermic decomposition of NO into N2 and O2. For Φ=0.3 the measured detonation velocity in a tube of 52 mm internal diameter is very much smaller than the calculated value and the mean size of the cellular structure is very much larger than the value extrapolated from data obtained with mixtures of higher but close equivalence ratio. All these results show that the detonation, though self-sustained and steady, is ‘non-ideal’, i.e. it is supported only by a part of the available chemical energy, that provided mainly by the first exothermic step. To cite this article: D. Desbordes et al., C. R. Mecanique 332 (2004). 相似文献
7.
This work focuses on interstitial solid solutions of hydrogen in the face-centred cubic (fcc) host lattice of palladium and nickel, using a first-principles based approach. Cluster Variation Method (CVM) and Monte Carlo simulation algorithms were especially designed, allowing a coupled use of both techniques, to study hydrogen–vacancy interactions inside an fcc metallic host lattice. First-principles calculations provided the H–Vac interaction energies by structure inversion method. The phase diagrams and thermodynamic properties were computed using only theoretical inputs. The mechanisms leading to the formation of the miscibility gaps observed for both Pd–H and Ni–H systems and the hydrogen ordering on palladium interstitial lattice were reproduced without any empirical term. 相似文献
8.
Nicolas P. Cheval Barbara Hoffmann Anna Dikova Fatih Sirindil Philippe Bertus Aurélien Blanc Jean-Marc Weibel Patrick Pale 《Tetrahedron》2018,74(50):7111-7119
Vinyl nosylates, readily obtained from β-dicarbonyl derivatives, could be efficiently engaged in Sonogashira cross-coupling reactions, either cocatalyzed by copper or silver salts. The para-nitrobenzenesulfonate (nosylate) group allows this coupling to be performed under very mild conditions (room temperature). These new leaving group and mild conditions could be applied to the synthesis of acetylenic coumarinyl derivatives and to the total synthesis of an acetylenic monoterpene natural product, named cleviolide. 相似文献
9.
A. Wnuk M. Kaczkan R. Piramidowicz R. Mahiou G. Bertrand M.-F. Joubert 《辐射效应与固体损伤》2013,168(1-6):469-473
The dynamics of up-conversion, green emission under excitation at different infra-red wavelength in Ho3? doped ZBLAN fiber is reported. Under infrared, 890 nm quasi cw pumping the complicated temporal behavior of the up-conversion signal is strongly influenced by the intermediate 5I5 state cross relaxation. The mechanisms of the observed up-conversion processes are proposed and the time evolution of the 5S2 population is described by the rate equation model. Parameters of the model are determined and numerical simulations of the excited state dynamics are performed. 相似文献
10.
Dr. Carmen E. Castillo Dr. Ilaria Gamba Laia Vicens Dr. Martin Clémancey Prof. Dr. Jean-Marc Latour Prof. Dr. Miquel Costas Prof. Dr. Manuel G. Basallote 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(15):4946-4954
Oxoiron(IV) complexes bearing tetradentate ligands have been extensively studied as models for the active oxidants in non-heme iron-dependent enzymes. These species are commonly generated by oxidation of their ferrous precursors. The mechanisms of these reactions have seldom been investigated. In this work, the reaction kinetics of complexes [FeII(CH3CN)2L](SbF6)2 ( [1](SbF6)2 and [2](SbF6)2 ) and [FeII(CF3SO3)2L] ( [1](OTf)2 and [2](OTf)2 ( 1 , L=Me,HPytacn; 2 , L=nP,HPytacn; R,R′Pytacn=1-[(6-R′-2-pyridyl)methyl]-4,7- di-R-1,4,7-triazacyclononane) with Bu4NIO4 to form the corresponding [FeIV(O)(CH3CN)L]2+ ( 3 , L=Me,HPytacn; 4 , L=nP,HPytacn) species was studied in acetonitrile/acetone at low temperatures. The reactions occur in a single kinetic step with activation parameters independent of the nature of the anion and similar to those obtained for the substitution reaction with Cl− as entering ligand, which indicates that formation of [FeIV(O)(CH3CN)L]2+ is kinetically controlled by substitution in the starting complex to form [FeII(IO4)(CH3CN)L]+ intermediates that are converted rapidly to oxo complexes 3 and 4 . The kinetics of the reaction is strongly dependent on the spin state of the starting complex. A detailed analysis of the magnetic susceptibility and kinetic data for the triflate complexes reveals that the experimental values of the activation parameters for both complexes are the result of partial compensation of the contributions from the thermodynamic parameters for the spin-crossover equilibrium and the activation parameters for substitution. The observation of these opposite and compensating effects by modifying the steric hindrance at the ligand illustrates so far unconsidered factors governing the mechanism of oxygen atom transfer leading to high-valent iron oxo species. 相似文献