全文获取类型
收费全文 | 452篇 |
免费 | 31篇 |
国内免费 | 1篇 |
专业分类
化学 | 312篇 |
晶体学 | 2篇 |
力学 | 28篇 |
数学 | 80篇 |
物理学 | 62篇 |
出版年
2024年 | 1篇 |
2023年 | 9篇 |
2022年 | 7篇 |
2021年 | 19篇 |
2020年 | 12篇 |
2019年 | 14篇 |
2018年 | 12篇 |
2017年 | 4篇 |
2016年 | 26篇 |
2015年 | 25篇 |
2014年 | 25篇 |
2013年 | 29篇 |
2012年 | 47篇 |
2011年 | 62篇 |
2010年 | 28篇 |
2009年 | 18篇 |
2008年 | 31篇 |
2007年 | 31篇 |
2006年 | 18篇 |
2005年 | 16篇 |
2004年 | 13篇 |
2003年 | 4篇 |
2002年 | 10篇 |
2001年 | 2篇 |
2000年 | 5篇 |
1999年 | 3篇 |
1998年 | 1篇 |
1997年 | 4篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1988年 | 1篇 |
1984年 | 1篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有484条查询结果,搜索用时 9 毫秒
11.
Pouzot M Nicolai T Benyahia L Durand D 《Journal of colloid and interface science》2006,293(2):376-383
Non-linear mechanical behavior at large shear deformation was been investigated for heat-set beta-lactoglobulin gels at pH 7 and 0.1 M NaCl using both oscillatory shear and shear flow. These gels have a self-similar structure at length scales smaller than the correlation length of the gel with fractal dimension d(f)=2. Strain hardening is observed that can be well described using the model proposed by Gisler et al. [T.C. Gisler, R.C. Ball, D.A. Weitz, Phys. Rev. Let. 82 (1999) 1064] for fractal colloidal gels. The increase of the shear modulus normalized by the low strain value (G(0)) is independent of G(0). For weak gels the elasticity increases up to a factor of ten, while for strong gels the increase is very small. At higher deformation irreversible fracture occurs, which leads eventually to macroscopic failure of the gel. For weak gels formed at low concentrations the deformation at failure is about 2, independent of the shear modulus. For strong gels fracture occurs at approximately constant stress (2 x 10(3) Pa). 相似文献
12.
Stijn Dekeukeleire Matthias D’hooghe Matthieu Vanwalleghem Willem Van Brabandt Norbert De Kimpe 《Tetrahedron》2012,68(52):10827-10834
Chiral piperazine and 1,4-diazepane annulated β-lactams, prepared from the corresponding (3R,4S)-4-imidoyl-1-(ω-haloalkyl)azetidin-2-ones through reduction with sodium borohydride in ethanol, were transformed into novel methyl (R)-alkoxy-[(S)-piperazin-2-yl]acetates and methyl (R)-alkoxy-[(S)-1,4-diazepan-2-yl]acetates upon treatment with hydrogen chloride in methanol. On the other hand, bromination of (3R,4R)-1-allyl-4-formyl-β-lactams and (3R,4S)-1-allyl-4-imidoyl-β-lactams in dichloromethane, followed by sodium borohydride reduction of the resulting dibrominated azetidin-2-ones in ethanol, did not afford the envisaged bicyclic β-lactams but unexpectedly furnished (3R,4S)-1-(2-bromo-2-propenyl)azetidin-2-ones instead. 相似文献
13.
David Gérard-Varet Matthieu Hillairet 《Archive for Rational Mechanics and Analysis》2010,195(2):375-407
We investigate the evolution of rigid bodies in a viscous incompressible fluid. The flow is governed by the 2D Navier–Stokes equations, set in a bounded domain with Dirichlet boundary conditions. The boundaries of the solids and the domain have Hölder regularity C 1,α , 0 < α ≦ 1. First, we show the existence and uniqueness of strong solutions up to the collision. A key ingredient is a BMO bound on the velocity gradient, which substitutes to the standard H 2 estimate for smoother domains. Then, we study the asymptotic behaviour of one C 1,α body falling over a flat surface. We show that a collision is possible in finite time if and only if α < 1/2. 相似文献
14.
Saidbakhrom Saidjalolov Dr. Zainab Edoo Dr. Matthieu Fonvielle Louis Mayer Dr. Laura Iannazzo Dr. Michel Arthur Prof. Dr. Mélanie Etheve-Quelquejeu Dr. Emmanuelle Braud 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(10):3542-3551
The carbapenem class of β-lactams has been optimized against Gram-negative bacteria producing extended-spectrum β-lactamases by introducing substituents at position C2. Carbapenems are currently investigated for the treatment of tuberculosis as these drugs are potent covalent inhibitors of l,d -transpeptidases involved in mycobacterial cell wall assembly. The optimization of carbapenems for inactivation of these unusual targets is sought herein by exploiting the nucleophilicity of the C8 hydroxyl group to introduce chemical diversity. As β-lactams are structure analogs of peptidoglycan precursors, the substituents were chosen to increase similarity between the drug and the substrate. Fourteen peptido-carbapenems were efficiently synthesized. They were more effective than the reference drug, meropenem, owing to the positive impact of a phenethylthio substituent introduced at position C2 but the peptidomimetics added at position C8 did not further improve the activity. Thus, position C8 can be modified to modulate the pharmacokinetic properties of highly efficient carbapenems. 相似文献
15.
Etienne Boutin Min Wang John C. Lin Matthieu Mesnage Daniela Mendoza Benedikt Lassalle‐Kaiser Christopher Hahn Thomas F. Jaramillo Marc Robert 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(45):16318-16322
Conversion of CO2 into valuable molecules is a field of intensive investigation with the aim of developing scalable technologies for making fuels using renewable energy sources. While electrochemical reduction into CO and formate are approaching industrial maturity, a current challenge is obtaining more reduced products like methanol. However, literature on the matter is scarce, and even more for the use of molecular catalysts. Here, we demonstrate that cobalt phthalocyanine, a well‐known catalyst for the electrochemical conversion of CO2 to CO, can also catalyze the reaction from CO2 or CO to methanol in aqueous electrolytes at ambient conditions of temperature and pressure. The studies identify formaldehyde as a key intermediate and an unexpected pH effect on selectivity. This paves the way for establishing a sequential process where CO2 is first converted to CO which is subsequently used as a reactant to produce methanol. Under ideal conditions, the reaction shows a global Faradaic efficiency of 19.5 % and chemical selectivity of 7.5 %. 相似文献
16.
Samia Amara Joël Toulc'Hoat Laure Timperman Agnès Biller Hervé Galiano Corinne Marcel Matthieu Ledigabel Prof. Mérièm Anouti 《Chemphyschem》2019,20(4):581-594
The development of a suitable functional electrolyte is urgently required for fast-charging and high-voltage alkali-ion (Li, Na, K) batteries as well as next-generation hybrids supercapacitors. Many recent works focused on an optimal selection of electrolytes for alkali-ion based systems and their electrochemical performance but the understanding of the fundamental aspect that explains their different behaviour is rare. Herein, we report a comparative study of transport properties for LiPF6, NaPF6, KPF6 in acetonitrile (AN) and a binary mixture of ethylene carbonate (EC), dimethyl carbonate (DMC): (EC/DMC : 1/1, weigh) through conductivities, densities and viscosities measurements in wide temperature domain. By application of the Stokes-Einstein, Nernst-Einstein, and Jones Dole equations, the effective ionic solvated radius of cation (reff), the ionic dissociation coefficient (αD) and structuring Jones Dole's parameters (A, B) for salt are calculated and discussed according to solvent or cation nature as a function of temperature. From the results, we demonstrate that better mobility of potassium can be explained by the nature of the ion-ion and ion-solvent interactions due to its polarizability. In the same time, the predominance of triple ions in the case of K+, is a disadvantage at high concentration. 相似文献
17.
Harrak Y Blaszykowski C Bernard M Cariou K Mainetti E Mouriès V Dhimane AL Fensterbank L Malacria M 《Journal of the American Chemical Society》2004,126(28):8656-8657
5-En-1-yn-3-ol substrates bearing a free hydroxyl group or an acyl group are highly versatile partners for PtCl2-catalyzed cycloisomerizations. Electrophilic activation of the alkyne moiety triggers at wish a hydride or an O-acyl migration yielding at the end to regioisomeric keto derivatives. The efficient preparation of Sabina ketone, an important monoterpene precursor, has been worked out. 相似文献
18.
Loumaigne M Vasanthakumar P Richard A Débarre A 《Physical chemistry chemical physics : PCCP》2011,13(24):11597-11605
The Brownian rotation of a nearly spherical gold particle capped with ligands can be observed in the correlation profile of the intensity of the two-photon excited luminescence. Here we report on a multi-parameter study of the luminescence properties, including spectral and polarization analysis of the signal at the single particle level. First, the data confirm the role of the radiative de-excitation of the surface plasmons in the luminescence process. Secondly, the results obtained at low power indicate that the capped particle in water can be approximatively described as a spherical rotor acting in the far-field as a point-like absorption and emission dipole of fixed directions. In addition, we show that the dynamics of the ligands, induced by the heat transfer from the particle to its environment, can be partly controlled by the choice of excitation wavelength. 相似文献
19.
20.
Mihaela Gulea Isabelle Abrunhosa Jozef Drabowicz Guillaume Grach Matthieu Hamel Serge Masson 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5-6):1267-1272
Abstract A new method to prepare enantioenriched sulfinates was developed to obtain optically active ortho-methylsulfinyl(phenylphosphonates). It consists of a diastereoselective oxidation of sulfenates to sulfinates. Additionally, preliminary results concerning the synthesis of ortho-phophonylated benzylic thiol derivatives via a new P═S to P═C [1,4]-rearrangement and a first synthetic application of these compounds are also described. 相似文献