全文获取类型
收费全文 | 3194篇 |
免费 | 167篇 |
国内免费 | 23篇 |
专业分类
化学 | 2270篇 |
晶体学 | 17篇 |
力学 | 175篇 |
数学 | 500篇 |
物理学 | 422篇 |
出版年
2024年 | 5篇 |
2023年 | 26篇 |
2022年 | 36篇 |
2021年 | 62篇 |
2020年 | 78篇 |
2019年 | 67篇 |
2018年 | 49篇 |
2017年 | 35篇 |
2016年 | 102篇 |
2015年 | 101篇 |
2014年 | 138篇 |
2013年 | 167篇 |
2012年 | 280篇 |
2011年 | 285篇 |
2010年 | 179篇 |
2009年 | 148篇 |
2008年 | 213篇 |
2007年 | 205篇 |
2006年 | 179篇 |
2005年 | 157篇 |
2004年 | 157篇 |
2003年 | 141篇 |
2002年 | 149篇 |
2001年 | 42篇 |
2000年 | 41篇 |
1999年 | 37篇 |
1998年 | 17篇 |
1997年 | 29篇 |
1996年 | 32篇 |
1995年 | 20篇 |
1994年 | 18篇 |
1993年 | 16篇 |
1992年 | 15篇 |
1991年 | 7篇 |
1990年 | 5篇 |
1989年 | 9篇 |
1987年 | 5篇 |
1986年 | 7篇 |
1985年 | 11篇 |
1984年 | 5篇 |
1983年 | 8篇 |
1982年 | 9篇 |
1981年 | 7篇 |
1980年 | 6篇 |
1979年 | 7篇 |
1978年 | 4篇 |
1977年 | 6篇 |
1976年 | 7篇 |
1968年 | 15篇 |
1967年 | 9篇 |
排序方式: 共有3384条查询结果,搜索用时 0 毫秒
111.
Functionalization of a Ruthenium–Diacetylide Organometallic Complex as a Next‐Generation Push–Pull Chromophore 下载免费PDF全文
Samuel De Sousa Dr. Laurent Ducasse Dr. Brice Kauffmann Prof. Thierry Toupance Dr. Céline Olivier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(23):7017-7024
The design and preparation of an asymmetric ruthenium–diacetylide organometallic complex was successfully achieved to provide an original donor–π–[M]–π–acceptor architecture, in which [M] corresponds to the [Ru(dppe)2] (dppe: bisdiphenylphosphinoethane) metal fragment. The charge‐transfer processes occurring upon photoexcitation of the push–pull metal–dialkynyl σ complex were investigated by combining experimental and theoretical data. The novel push–pull complex, appropriately end capped with an anchoring carboxylic acid function, was further adsorbed onto a semiconducting metal oxide porous thin film to serve as a photosensitizer in hybrid solar cells. The resulting photoactive material, when embedded in dye‐sensitized solar cell devices, showed a good spectral response with a broad incident photon‐to‐current conversion efficiency profile and a power conversion efficiency that reached 7.3 %. Thus, this material paves the way to a new generation of organometallic chromophores for photovoltaic applications. 相似文献
112.
Michael Koch Karthikeyan Perumal Dr. Olivier Blacque Dr. Jai Anand Garg Dr. Ramanathan Saiganesh Dr. Senthamaraikannan Kabilan Prof. Dr. Kallupattu Kuppusamy Balasubramanian Dr. Koushik Venkatesan 《Angewandte Chemie (International ed. in English)》2014,53(25):6378-6382
Design of highly efficient phosphorescent emitters based on metal‐ and heavy atom‐free boron compounds has been demonstrated by taking advantage of the singlet fission process. The combination of a suitable molecular scaffold and appropriate electronic nature of the substituents has been utilized to tailor the phosphorescence emission properties in solution, neat solid, and in doped PMMA thin films. 相似文献
113.
Charif Tamin Denis Chaumont Olivier Heintz Mohamed Adnane 《Surface and interface analysis : SIA》2020,52(12):985-990
This paper aims to estimate the band alignment to CdS/CZTS hetero-interface by direct X-ray photoelectron spectroscopy (XPS) measurements. XPS was used to determinate the valence-band offset (VBO) directly by determining the valence band positions at the hetero-interface. The conduction band offset (CBO) value was estimated based on the band gap measurements by UV/Visible spectroscopy and VBO measurements. The position of valence band (VB) changes close to the CdS-CZTS interface and the CBO is cliff-like. The band alignment diagram indicates that the CdS-CZTS interface heterojunction is type II. 相似文献
114.
Jompol Thongpaen Romane Manguin Olivier Basl 《Angewandte Chemie (International ed. in English)》2020,59(26):10242-10251
The asymmetric functionalization of C?H bond is a particularly valuable approach for the production of enantioenriched chiral organic compounds. Chiral N‐heterocyclic carbene (NHC) ligands have become ubiquitous in enantioselective transition‐metal catalysis. Conversely, the use of chiral NHC ligands in metal‐catalyzed asymmetric C?H bond functionalization is still at an early stage. This minireview highlights all the developments and the new advances in this rapidly evolving research area. 相似文献
115.
Adam Ashcraft Kaixuan Liu Arindam Mukhopadhyay Victor Paulino Chuan Liu Brianna Bernard Dalia Husainy Tina Phan Jean‐Hubert Olivier 《Angewandte Chemie (International ed. in English)》2020,59(19):7487-7493
Locking‐in the conformation of supramolecular assemblies provides a new avenue to regulate the (opto)electronic properties of robust nanoscale objects. In the present contribution, we show that the covalent tethering of a perylene bisimide (PBI)‐derived supramolecular polymer with a molecular locker enables the formation of a locked superstructure equipped with emergent structure–function relationships. Experiments that exploit variable‐temperature ground‐state electronic absorption spectroscopy unambiguously demonstrate that the excitonic coupling between nearest neighboring units in the tethered superstructure is preserved at a temperature (371 K) where the pristine, non‐covalent assembly exists exclusively in a molecularly dissolved state. A close examination of the solid‐state morphologies reveals that the locked superstructure engenders the formation of hierarchical 1D materials which are not achievable by unlocked assemblies. To complement these structural attributes, we further demonstrate that covalently tethering a supramolecular polymer built from PBI subunits enables the emergence of electronic properties not evidenced in non‐covalent assemblies. Using cyclic voltammetry experiments, the elucidation of the potentiometric properties of the locked superstructure reveals a 100‐mV stabilization of the conduction band energy when compared to that recorded for the non‐covalent assembly. 相似文献
116.
Guangcan Xu Sbastien Leloux Pinglu Zhang Jorge Meijide Surez Yongmin Zhang Etienne Derat Mickaël Mnand Olivia Bistri‐Aslanoff Sylvain Roland Tom Leyssens Olivier Riant Matthieu Sollogoub 《Angewandte Chemie (International ed. in English)》2020,59(19):7591-7597
The encapsulation of copper inside a cyclodextrin capped with an N‐heterocyclic carbene (ICyD) allowed both to catch the elusive monomeric (L)CuH and a cavity‐controlled chemoselective copper‐catalyzed hydrosilylation of α,β‐unsaturated ketones. Remarkably, (α‐ICyD)CuCl promoted the 1,2‐addition exclusively, while (β‐ICyD)CuCl produced the fully reduced product. The chemoselectivity is controlled by the size of the cavity and weak interactions between the substrate and internal C?H bonds of the cyclodextrin. 相似文献
117.
Faure Thierry M. Dumas Laurent Montagnier Olivier 《Theoretical and Computational Fluid Dynamics》2020,34(1):79-103
Theoretical and Computational Fluid Dynamics - The aerodynamic characteristics of two neighboring airfoils are greatly different from those of a single airfoil, for both attached and detached flow... 相似文献
118.
Paul Thiry Olivier Nocent Fabien Buisseret William Bertucci Andr Thvenon Emilie Simoneau-Buessinger 《Entropy (Basel, Switzerland)》2022,24(4)
Low back pain (LBP) obviously reduces the quality of life but is also the world’s leading cause of years lived with disability. Alterations in motor response and changes in movement patterns are expected in LBP patients when compared to healthy people. Such changes in dynamics may be assessed by the nonlinear analysis of kinematical time series recorded from one patient’s motion. Since sample entropy (SampEn) has emerged as a relevant index measuring the complexity of a given time series, we propose the development of a clinical test based on SampEn of a time series recorded by a wearable inertial measurement unit for repeated bending and returns (b and r) of the trunk. Twenty-three healthy participants were asked to perform, in random order, 50 repetitions of this movement by touching a stool and another 50 repetitions by touching a box on the floor. The angular amplitude of the b and r movement and the sample entropy of the three components of the angular velocity and acceleration were computed. We showed that the repetitive b and r “touch the stool” test could indeed be the basis of a clinical test for the evaluation of low-back-pain patients, with an optimal duration of 70 s, acceptable in daily clinical practice. 相似文献
119.
Monitoring and Quantifying the Passive Transport of Molecules Through Patch–Clamp Suspended Real and Model Cell Membranes 下载免费PDF全文
Dr. Pierluca Messina Dr. Frédéric Lemaître Prof. François Huet Dr. Kieu An Ngo Dr. Vincent Vivier Prof. Eric Labbé Dr. Olivier Buriez Prof. Christian Amatore 《Angewandte Chemie (International ed. in English)》2014,53(12):3192-3196
Transport of active molecules across biological membranes is a central issue for the success of many pharmaceutical strategies. Herein, we combine the patch–clamp principle with amperometric detection for monitoring fluxes of redox‐tagged molecular species across a suspended membrane patched from a macrophage. Solvent‐ and protein‐free lipid bilayers (DPhPC, DOPC, DOPG) patched from single‐wall GUV have been thoroughly investigated and the corresponding fluxes measurements quantified. The quality of the patches and their proper sealing were successfully characterized by electrochemical impedance spectroscopy. This procedure appears versatile and perfectly adequate to allow the investigation of transport and quantification of the transport properties through direct measurement of the coefficients of partition and diffusion of the compound in the membrane, thus offering insight on such important biological and pharmacological issues. 相似文献
120.
Dr. Tao Liu Dr. Aline Nonat Dr. Maryline Beyler Dr. Martín Regueiro‐Figueroa Dr. Katia Nchimi Nono Dr. Olivier Jeannin Dr. Franck Camerel Dr. François Debaene Dr. Sarah Cianférani‐Sanglier Prof. Raphaël Tripier Dr. Carlos Platas‐Iglesias Dr. Loïc J. Charbonnière 《Angewandte Chemie (International ed. in English)》2014,53(28):7259-7263
Lanthanide complexes (Ln=Eu, Tb, and Yb) that are based on a C2‐symmetric cyclen scaffold were prepared and characterized. The addition of fluoride anions to aqueous solutions of the complexes resulted in the formation of dinuclear supramolecular compounds in which the anion is confined into the cavity that is formed by the two complexes. The supramolecular assembly process was monitored by UV/Vis absorption, luminescence, and NMR spectroscopy and high‐resolution mass spectrometry. The X‐ray crystal structure of the europium dimer revealed that the architecture of the scaffold is stabilized by synergistic effects of the Eu? F? Eu bridging motive, π stacking interactions, and a four‐component hydrogen‐bonding network, which control the assembly of the two [EuL] entities around the fluoride ion. The strong association in water allowed for the luminescence sensing of fluoride down to a detection limit of 24 nM . 相似文献