全文获取类型
收费全文 | 703篇 |
免费 | 35篇 |
国内免费 | 3篇 |
专业分类
化学 | 508篇 |
晶体学 | 4篇 |
力学 | 17篇 |
数学 | 96篇 |
物理学 | 116篇 |
出版年
2023年 | 8篇 |
2022年 | 17篇 |
2021年 | 26篇 |
2020年 | 21篇 |
2019年 | 23篇 |
2018年 | 20篇 |
2017年 | 12篇 |
2016年 | 33篇 |
2015年 | 28篇 |
2014年 | 19篇 |
2013年 | 49篇 |
2012年 | 51篇 |
2011年 | 50篇 |
2010年 | 33篇 |
2009年 | 33篇 |
2008年 | 47篇 |
2007年 | 50篇 |
2006年 | 42篇 |
2005年 | 39篇 |
2004年 | 24篇 |
2003年 | 22篇 |
2002年 | 21篇 |
2001年 | 6篇 |
2000年 | 6篇 |
1999年 | 3篇 |
1997年 | 4篇 |
1996年 | 1篇 |
1995年 | 6篇 |
1994年 | 1篇 |
1993年 | 9篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1986年 | 1篇 |
1985年 | 6篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1957年 | 1篇 |
1940年 | 1篇 |
1935年 | 3篇 |
1906年 | 1篇 |
排序方式: 共有741条查询结果,搜索用时 31 毫秒
31.
32.
Castro Jorge Fernández Francisco Olivares Felipe Berríos Cristhian Garrido-Ramírez Elizabeth Blanco Elodie Escalona Néstor Aspée Alexis Barrías Pablo Ureta-Zañartu M. Soledad 《Journal of Solid State Electrochemistry》2021,25(1):117-131
Journal of Solid State Electrochemistry - 2,4,6-trichlorophenol (TCP) is a persistent pollutant introduced in water by industrial processes and pesticides. We have studied the electrooxidation of... 相似文献
33.
34.
Using experiments and theory, we show that light scattering by inhomogeneities in the index of refraction of a fluid can drive a large-scale flow. The experiment uses a near-critical, phase-separated liquid, which experiences large fluctuations in its index of refraction. A laser beam traversing the liquid produces a interface deformation on the scale of the experimental setup and can cause a liquid jet to form. We demonstrate that the deformation is produced by a scattering-induced flow by obtaining good agreements between the measured deformations and those calculated assuming this mechanism. 相似文献
35.
Homogeneous and unimolecular gas‐phase thermal decomposition kinetics of methyl benzoylformate: experimental and theoretical study
下载免费PDF全文
![点击此处可从《Journal of Physical Organic Chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Yeljair Monascal Alexis Maldonado José R. Mora Tania Córdova Gabriel Chuchani 《Journal of Physical Organic Chemistry》2015,28(1):40-46
The kinetics of the gas‐phase thermal decomposition of the α‐ketoester methyl benzoylformate was carried out in a static system with reaction vessel deactivated with allyl bromide, and in the presence of the free radical inhibitor propene. The rate coefficients were determined over the temperature range of 440–481 °C and pressures from 32 to 80 Torr. The reaction was found to be homogenous, unimolecular and obey a first‐order rate law. The products are methyl benzoate and CO. The temperature dependence of the rate coefficient gives the following Arrhenius parameters: log10 k (s?1) = 13.56 ± 0.31 and Ea (kJ mol?1) = 232.6 ± 4.4. Theoretical calculations of the kinetic and thermodynamic parameters are in good agreement with the experimental values using PBE1PBE/6‐311++g(d,p). A theoretical Arrhenius plot was constructed at this level of theory, and the good agreement with the experimental Arrhenius plot suggests that this model of transition state may describe reasonably the elimination process. These results suggest a concerted non‐synchronous semi‐polar three‐membered cyclic transition state type of mechanism. The most advanced coordinate is the bond breaking Cδ+‐‐‐δ‐OCH3 with an evolution of 66.7%, implying this as the limiting factor of the elimination process. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
36.
Gas‐phase elimination kinetics of selected aliphatic α,β‐unsaturated aldehydes catalyzed by hydrogen chloride
下载免费PDF全文
![点击此处可从《Journal of Physical Organic Chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Libia L. Julio José R. Mora Alexis Maldonado Gabriel Chuchani 《Journal of Physical Organic Chemistry》2015,28(4):261-265
The gas‐phase elimination of 2‐methyl‐2‐propenal catalyzed by HCl yields propene and CO gas, while E‐2‐pentenal with the same catalyst gives butene and CO gas. The kinetics determinations were carried out in a static system with the reaction vessels deactivated with allyl bromide and the presence of the free radical inhibitor toluene. Temperature and pressure ranges were 350.0–410.0 °C and 34–76 Torr. The elimination reactions are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients for the reactions are expressible by the following Arrhenius equations: Data from the kinetic and thermodynamic parameters of these catalyzed elimination reactions implies a mechanism of a concerted five‐membered cyclic transition state structure for the formation of the corresponding olefin and carbon monoxide. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
37.
Camille Flament Joël Ribis Jérôme Garnier Thierry Vandenberghe Jean Henry Alexis Deschamps 《哲学杂志》2015,95(8):906-917
The age hardening 6061-T6 aluminium alloy has been chosen as structural material for the core vessel of the material testing Jules Horowitz nuclear reactor. The alloy contains incoherent Al(Cr, Fe, Mn)Si dispersoids whose characterization by energy-filtered transmission electron microscopy (EFTEM) analysis shows a core/shell organization tendency where the core is (Mn, Fe) rich, and the shell is Cr rich. The present work studies the stability of this organization under irradiation. TEM characterization on the same particles, before and after 1 MeV electron irradiation, reveals that the core/shell organization is enhanced after irradiation. It is proposed that the high level of point defects, created by irradiation, ensures a radiation-enhanced diffusion process favourable to the unmixing forces between (Fe, Mn) and Cr. Shell formation may result in the low-energy interface segregation of Cr atoms within the (Fe, Mn) system combined with the unmixing of Cr, Fe and Mn components. 相似文献
38.
A Direct CH/ArH Coupling Approach to Oxindoles,Thio‐oxindoles, 3,4‐Dihydro‐1 H‐quinolin‐2‐ones,and 1,2,3,4‐Tetrahydroquinolines
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Timothy E. Hurst Ryan M. Gorman Pauline Drouhin Dr. Alexis Perry Prof. Richard J. K. Taylor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(43):14063-14073
A copper(II)‐catalysed approach to oxindoles, thio‐oxindoles, 3,4‐dihydro‐1H‐quinolin‐2‐ones, and 1,2,3,4‐tetrahydroquinolines via formal C?H, Ar?H coupling is described. In a new variant, copper(II) 2‐ethylhexanoate has been identified as an inexpensive and efficient catalyst for this transformation, which utilises atmospheric oxygen as the re‐oxidant. 相似文献
39.
Functionalized Graphene as a Gatekeeper for Chiral Molecules: An Alternative Concept for Chiral Separation
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Andreas W. Hauser Narbe Mardirossian Julien A. Panetier Martin Head‐Gordon Alexis T. Bell Peter Schwerdtfeger 《Angewandte Chemie (International ed. in English)》2014,53(37):9957-9960
We propose a new method of chiral separation using functionalized nanoporous graphene as an example. Computational simulations based on density functional theory show that the attachment of a suitable chiral “bouncer” molecule to the pore rim prevents the passage of the undesired enantiomer while letting its mirror image through. 相似文献
40.
Khalil Yamani Hugo Pierre Dr. Alexis Archambeau Dr. Christophe Meyer Prof. Dr. Janine Cossy 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18663-18667
Catalytic enantioselective access to disubstituted functionalized gem-difluorocyclopropanes, which are emerging fluorinated motifs of interest in medicinal chemistry, was achieved through asymmetric transfer hydrogenation of gem-difluorocyclopropenyl esters, catalyzed by a Noyori–Ikariya (p-cymene)-ruthenium(II) complex, with (N-tosyl-1,2-diphenylethylenediamine) as the chiral ligand and isopropanol as the hydrogen donor. The resulting cis-gem-difluorocyclopropyl esters were obtained with moderate to high enantioselectivity (ee=66–99 %), and post-functionalization reactions enable access to valuable building blocks incorporating a cis- or trans-gem-difluorocyclopropyl motif. 相似文献