全文获取类型
收费全文 | 442篇 |
免费 | 31篇 |
国内免费 | 1篇 |
专业分类
化学 | 303篇 |
晶体学 | 2篇 |
力学 | 28篇 |
数学 | 80篇 |
物理学 | 61篇 |
出版年
2024年 | 1篇 |
2023年 | 9篇 |
2022年 | 7篇 |
2021年 | 18篇 |
2020年 | 12篇 |
2019年 | 14篇 |
2018年 | 12篇 |
2017年 | 4篇 |
2016年 | 25篇 |
2015年 | 24篇 |
2014年 | 25篇 |
2013年 | 28篇 |
2012年 | 46篇 |
2011年 | 61篇 |
2010年 | 28篇 |
2009年 | 18篇 |
2008年 | 30篇 |
2007年 | 30篇 |
2006年 | 18篇 |
2005年 | 16篇 |
2004年 | 12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 |
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474条查询结果,搜索用时 15 毫秒
11.
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
12.
13.
Manon Réau Florent Langenfeld Jean-François Zagury Matthieu Montes 《Journal of computer-aided molecular design》2018,32(1):231-238
The Drug Design Data Resource (D3R) Grand Challenges are blind contests organized to assess the state-of-the-art methods accuracy in predicting binding modes and relative binding free energies of experimentally validated ligands for a given target. The second stage of the D3R Grand Challenge 2 (GC2) was focused on ranking 102 compounds according to their predicted affinity for Farnesoid X Receptor. In this task, our workflow was ranked 5th out of the 77 submissions in the structure-based category. Our strategy consisted in (1) a combination of molecular docking using AutoDock 4.2 and manual edition of available structures for binding poses generation using SeeSAR, (2) the use of HYDE scoring for pose selection, and (3) a hierarchical ranking using HYDE and MM/GBSA. In this report, we detail our pose generation and ligands ranking protocols and provide guidelines to be used in a prospective computer aided drug design program. 相似文献
14.
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
15.
Raúl Pérez-Ruiz Robert Fichtler Yrene Diaz Miara Matthieu Nicoul Dominik Schaniel Helfried Neumann Matthias Beller Dirk Blunk Axel G. Griesbeck Axel Jacobi von Wangelin 《Journal of fluorescence》2010,20(3):657-664
The photophysical properties of a series of structurally related 4-aminophthalimides and the corresponding 5-aminophthalic hydrazides (luminols) are reported. Absorption, steady-state, and time-resolved fluorescence spectra of luminols exhibited substitution, solvent, and pH dependence. Singlet lifetimes have been determined by time-resolved laser flash spectroscopy. UV spectra in gas phase and DMSO solution were calculated by TD-DFT which revealed the existence of two low-energy excited singlet states with strong pH-sensitivity. 相似文献
16.
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
17.
18.
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
19.
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
20.
Ina Reiche Matthieu Lebon Céline Chadefaux Katharina Müller Anne-Solenn Le Hô Michael Gensch Ulrich Schade 《Analytical and bioanalytical chemistry》2010,397(6):2491-2499
Archaeological bone materials record characteristic markers of life in prehistoric times (dating, climate, environment, diet, human migration) in their isotopic and chemical composition in addition to palaeontological, archaeozoological, anthropological and palaeogenetic information. Thus, the discovery and conservation of archaeological bone materials is of great importance to get access to this information. However, archaeological materials are altered by different postmortem processes and it appears necessary to estimate if the archaeological information is still reliable or if it has been modified during burial. As archaeological bone materials present a high structural hierarchy at the micro- and nanoscale, changes induced by diagenetic phenomena have to be observed at these scales. One method for revealing post mortem changes of the bone structure and composition at the microscale is synchrotron radiation micro-FTIR imaging (SR micro-FTIR). Thus, thin sections of about 5,000-year-old archaeological bones have been analysed in transmission mode at the IRIS beamline (BESSY II, HZB Berlin) to determine markers of the state of bone preservation at the microscale. The archaeological bone material comes from station 19 of the Neolithic site of the Chalain Lake. By using SR micro-FTIR it was possible to image characteristic bone structures, e.g. osteons (the constitutive histological unit of cortical bone), using the absorption band ratios corresponding to different chemical bone constituents (collagen content and quality, phosphate crystallinity, carbonate content). These data allow us to precisely evaluate the state of preservation of a 5,000-year-old bone at the histological level. Figure
Chemical mapping of a thin section of the archaeological bone AB_CH19nb1 from the Neolithic station 19 at Chalain Lake 相似文献