全文获取类型
收费全文 | 706篇 |
免费 | 51篇 |
国内免费 | 2篇 |
专业分类
化学 | 541篇 |
晶体学 | 1篇 |
力学 | 23篇 |
数学 | 80篇 |
物理学 | 114篇 |
出版年
2023年 | 9篇 |
2022年 | 7篇 |
2021年 | 9篇 |
2020年 | 20篇 |
2019年 | 13篇 |
2018年 | 23篇 |
2017年 | 5篇 |
2016年 | 38篇 |
2015年 | 22篇 |
2014年 | 28篇 |
2013年 | 35篇 |
2012年 | 60篇 |
2011年 | 80篇 |
2010年 | 39篇 |
2009年 | 47篇 |
2008年 | 64篇 |
2007年 | 69篇 |
2006年 | 55篇 |
2005年 | 52篇 |
2004年 | 24篇 |
2003年 | 26篇 |
2002年 | 17篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 1篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1981年 | 1篇 |
排序方式: 共有759条查询结果,搜索用时 15 毫秒
1.
Quentin Dherbassy Srimanta Manna Fabien J. T. Talbot Watcharapon Prasitwatcharakorn Gregory J. P. Perry David J. Procter 《Chemical science》2020,11(42):11380
The copper-catalyzed functionalization of enyne derivatives has recently emerged as a powerful approach in contemporary synthesis. Enynes are versatile and readily accessible substrates that can undergo a variety of reactions to yield densely functionalized, enantioenriched products. In this perspective, we review copper-catalyzed transformations of enynes, such as boro- and hydrofunctionalizations, copper-mediated radical difunctionalizations, and cyclizations. Particular attention is given to the regiodivergent functionalization of 1,3-enynes, and the current mechanistic understanding of such processes.The copper-catalyzed functionalization of enynes is a powerful approach to yield densely functionalized products. This review covers various transformations, such as boro- and hydrofunctionalizations, copper-mediated radical difunctionalizations, and cyclizations. 相似文献
2.
Gas‐phase conformations of capistruin – comparison of lasso,branched‐cyclic and linear topologies 下载免费PDF全文
3.
Dr. Jagadeesh Yerri Dr. José Dias Dr. Mallikajurna Reddy Nimmakayala Franck Razafindrainibe Charlotte Courageux Anne-Julie Gastellier Johanne Jegoux Dr. Caroline Coisne Dr. Christophe Landry Dr. Fabien Gosselet Johan Hachani Dr. Jean-François Goossens Prof. Marie-Pierre Dehouck Dr. Florian Nachon Dr. Rachid Baati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):15035-15044
Novel 6-alkyl- and 6-alkenyl-3-fluoro-2-pyridinaldoximes have been synthesised by using a mild and efficient chemoselective hydrogenation of 6-alkynyl-3-fluoro-2-pyridinaldoxime scaffolds, without altering the reducible, unprotected, sensitive oxime functionality and the C−F bond. These novel 6-alkyl-3-fluoro-2-pyridinaldoximes may find medicinal application as antidotes to organophosphate poisoning. Indeed, one low-molecular-weight compound exhibited increased affinity for sarin-inhibited acetylcholinesterase (hAChE) and greater reactivation efficiency or resurrection for sarin-inhibited hAChE, compared with those of 2-pyridinaldoxime (2-PAM) and 1-({[4-(aminocarbonyl)pyridinio]methoxy}methyl)-2-[(hydroxyimino)methyl]pyridinium chloride (HI-6), two pyridinium salts currently used as antidote by several countries. In addition, the uncharged 3-fluorinated bifunctional hybrid showed increased in vitro blood–brain barrier permeability compared with those of 2-PAM, HI-6 and obidoxime. These promising features of novel low-molecular-weight alkylfluoropyridinaldoxime open up a new era for the design, synthesis and discovery of central non-quaternary broad spectrum reactivators for organophosphate-inhibited cholinesterases. 相似文献
4.
Chaimae Bariki Fabien Halter Fabien Thiesset Christian Chauveau Iskender Gökalp Ketana Teav Sina Kheirkhah Adam M. Steinberg 《Proceedings of the Combustion Institute》2019,37(2):1911-1918
Simultaneous measurements of temperature, CH* and OH* chemiluminescent species are carried out to explore the impact of stretch rate and curvature on the structure of premixed flames. The configuration of an initially flat premixed flame interacting with a toroidal vortex is selected for the present study and reasons for this choice are discussed. Lewis number effects are assessed by comparing methane and propane flames. It is emphasized that the flame structure experiences very strong variations. In particular, the flame is shrunk (broadened) in the initial (final) period of the interaction with the vortex where strain rate (curvature) contribution of the stretch rate is predominant. By further analysing independently the thickness of the preheat and reaction zones, it is shown that for propane flames, not only the former but also the latter is significantly altered in zones where the flame curvature is negative. Changes in the reaction zone properties are further emphasized using CH* and OH* radicals. It is demonstrated that higher thermal diffusivity plays a significant role around curved regions, in which the enhanced diffusion of heat leads to a strong increase of CH* compared to OH* intensity. As an overall conclusion, this study suggests that it would be interesting to reassess the internal flame structure at lower and moderate Karlovitz numbers since changes might appear for a moderate vortex intensity with typical size much larger than the flame thickness. 相似文献
5.
Daniel Grinberg Sabrina Siddique Minh‐Quyen Le Richard Liang Jean‐Fabien Capsal Pierre‐Jean Cottinet 《Journal of Polymer Science.Polymer Physics》2019,57(2):109-115
Additive manufacturing (AM), otherwise known as three‐dimensional (3D) printing, is driving major innovations in many areas, such as engineering, manufacturing, art, education, and medicine. Although a considerable amount of progress has been made in this field, additional research work is required to overcome various remaining challenges. Recently, one of the actively researched areas lies in the AM of smart materials and structures. Electroactive materials incorporated in 3D printing have given birth to 4D printing, where 3D printed structures can perform as actuating and/or sensing systems, making it possible to deliver electrical signals under external mechanical stimuli and vice versa. In this paper, we present a lightweight, low cost piezoelectric material based on the dispersion of inorganic ferroelectric submicron particles in a polymer matrix. We report on how the proposed material is compatible with the AM process. Finally, we discuss its potential applications for healthcare, especially in smart implants prostheses. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 109–115 相似文献
6.
7.
Emeline Appert Dr. Agnès Martin-Mingot Dr. Omar Karam Dr. Fabien Zunino Dr. Bastien Michelet Dr. Fodil Bouazza Prof. Sébastien Thibaudeau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(49):e202201583
The field of medicinal chemistry is currently witnessing a deuterium rush owing to the remarkable properties of this element as bioisoster of hydrogen atom. Aromatic hydrogen isotope exchange (HIE) is one of the most studied strategies nowadays as it promises to access deuterium-modified drugs directly from their non-labeled parents. While most of the recent studies focus on metal-catalyzed C−H activation strategy, the use of superacidic conditions has been largely overlooked. This study shows that the use of TfOD as reaction medium allows the late-stage polydeuteration of a broad library of pharmaceuticals bearing a wide array of functional groups, complementing existing procedures. 相似文献
8.
Dr. David F. León Rayo Ali Mansour Dr. Wenbin Wu Dr. Benjamin N. Bhawal Prof. Fabien Gagosz 《Angewandte Chemie (International ed. in English)》2023,62(3):e202212893
Direct C−H bond functionalization is a useful strategy for the straightforward formation of C−C and C−Heteroatom bonds. In the present work, a unique approach for the challenging electrophilic Au-catalyzed α-C−H bond functionalization of tertiary amines is presented. Electronic, steric and conformational synergistic effects exerted by the use of a malonate unit in the substrate were key to the success of this transformation. This new reactivity was applied to the synthesis of tetrahydro-γ-carboline products which, under oxidative conditions, could be converted into valuable structural motifs found in bioactive alkaloid natural products. 相似文献
9.
Fabien Pascale Klaus Doll Francesco Silvio Gentile Roberto Dovesi 《Journal of computational chemistry》2023,44(2):65-75
The ferromagnetic and antiferromagnetic wave functions of the KMnF3 perovskite have been evaluated quantum-mechanically by using an all electron approach and, for comparison, pseudopotentials on the transition metal and the fluorine ions. It is shown that the different number of α and β electrons in the d shell of Mn perturbs the inner shells, with shifts between the α and β eigenvalues that can be as large as 6 eV for the 3s level, and is far from negligible also for the 2s and 2p states. The valence electrons of F are polarized by the majority spin electrons of Mn, and in turn, spin polarize their 1s electrons. When a pseudopotential is used, such a spin polarization of the core functions of Mn and F can obviously not take place. The importance of such a spin polarization can be appreciated by comparing (i) the spin density at the Mn and F nuclear position, and then the Fermi contact constant, a crucial quantity for the hyperfine coupling, and (ii) the ferromagnetic–antiferromagnetic energy difference, when obtained with an all electron or a pseudopotential scheme, and exploring how the latter varies with pressure. This difference is as large as 50% of the all electron datum, and is mainly due to the rigid treatment of the F ion core. The effect of five different functionals on the core spin polarization is documented. 相似文献
10.
Chrystelle Neaime Dr. Carole Daiguebonne Dr. Guillaume Calvez Stéphane Freslon Dr. Kevin Bernot Dr. Fabien Grasset Dr. Stéphane Cordier Prof. Olivier Guillou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17466-17473
Heteronuclear lanthanide‐based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare‐earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non‐toxic polyols. Bulk powders of the formula [Ln2?2xLn′2x(bdc)3 ? 4 H2O]∞ (where H2bdc denotes 1,4‐benzene‐dicarboxylic acid, 0≤x≤1, and Ln and Ln′ denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light‐scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide‐based coordination polymers. 相似文献