全文获取类型
收费全文 | 520篇 |
免费 | 24篇 |
国内免费 | 2篇 |
专业分类
化学 | 363篇 |
晶体学 | 1篇 |
力学 | 17篇 |
数学 | 75篇 |
物理学 | 90篇 |
出版年
2024年 | 1篇 |
2023年 | 8篇 |
2022年 | 15篇 |
2021年 | 24篇 |
2020年 | 19篇 |
2019年 | 17篇 |
2018年 | 15篇 |
2017年 | 7篇 |
2016年 | 30篇 |
2015年 | 22篇 |
2014年 | 16篇 |
2013年 | 27篇 |
2012年 | 37篇 |
2011年 | 35篇 |
2010年 | 23篇 |
2009年 | 22篇 |
2008年 | 38篇 |
2007年 | 38篇 |
2006年 | 27篇 |
2005年 | 33篇 |
2004年 | 19篇 |
2003年 | 20篇 |
2002年 | 14篇 |
2001年 | 3篇 |
2000年 | 4篇 |
1999年 | 3篇 |
1997年 | 2篇 |
1995年 | 4篇 |
1994年 | 1篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 3篇 |
1987年 | 1篇 |
1985年 | 2篇 |
1983年 | 1篇 |
1978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546条查询结果,搜索用时 0 毫秒
41.
Parenty AD Smith LV Pickering AL Long DL Cronin L 《The Journal of organic chemistry》2004,69(18):5934-5946
A new class of phenanthridinium derivative has been isolated from the reaction of 2-bromoethyl-phenanthridinium bromide with a range of primary amines in excellent yields. The reaction pathway is unprecedented and proceeds via three cascade steps: nucleophilic attack of a primary amine on the iminium moiety of a heteroaromatic ring system and cyclization to form a five-membered ring, followed by hydride loss to yield a rearomatized dihydro-1H-imidazo[1,2-f]phenanthridinium derivative. A range of NMR phase transfer experiments were carried out to elucidate the mechanistic pathway, and the methodology has been further developed by means of a biphasic system using N-bromosuccinimide as a co-oxidizing agent. The method has also been extended to other N-heterocyclic cation derivatives such as quinolinium and quinazolinium. 相似文献
42.
Vakros J Bourikas K Perlepes S Kordulis C Lycourghiotis A 《Langmuir : the ACS journal of surfaces and colloids》2004,20(24):10542-10550
Diffuse reflectance spectroscopy was used for the first time to investigate the adsorption of the [Co(H2O)6]2+ ions on the interface developed between the surface of the gamma-alumina particles and the electrolytic aqueous solutions used for the preparation of cobalt-supported gamma-alumina catalysts by equilibrium deposition filtration. The formation of inner-sphere Co(II) surface complexes in which Co(II) is in octahedral symmetry was confirmed. A deconvolution peak centered at approximately 585 nm was attributed to the exchange of one aqua ligand with one AlxOHy (x = 1, 2, or 3; y = 0 or 1) negatively charged surface group resulting in the formation of mononuclear monosubstituted inner-sphere Co(II) complexes at a Co(II) surface concentration equal to 0.02 micromol of Co(II)/m2. It was inferred that as the surface Co(II) concentration increases the formation of disubstituted and/or trisubstituted surface complexes is favored with respect to the formation of monosubstituted Co(II) surface complexes. A deconvolution peak centered at approximately 640 nm was attributed to the exchange of one or more aqua ligands with bridging hydroxo ligands (Co-O-H). The relative magnitude of this peak increases with the Co(II) surface concentration, reflecting the increasing formation of binuclear, oligonuclear, and multinuclear Co(II) surface complexes and then the formation of the Co(II) surface precipitate. 相似文献
43.
Mukhopadhyay S Zerella M Bell AT Srinivas RV Smith GS 《Chemical communications (Cambridge, England)》2004,(4):472-473
Methane is transformed selectively to methanesulfonyl chloride at low temperature by liquid-phase reaction of methane with SO(2)Cl(2) in the presence of a free radical initiator and a promoter using 100% H(2)SO(4) as the solvent. 相似文献
44.
Rabindra N. Roy Lakshmi N. Roy Kathleen A. Allen Casey J. Mehrhoff Isaac B. Henson Jessica M. Stegner Alexis L. Jenkins Ankita A. Shah Stephen D. Rocchio 《Journal of solution chemistry》2012,41(6):1044-1053
In this study, we report the pH values of two buffer solutions without chloride ion and eight buffer solutions with NaCl with an ionic strength I=0.16 mol?kg?1. Electromotive force (emf) techniques have been used to get the cell potentials at 12 temperatures from 5 to 55?°C, including 37?°C. An extended form of the Bates-Guggenheim convention is used in the entire ionic strength range, 0.04 to 0.16?mol?kg?1. The residual liquid junction potentials (??E j ) of the buffer solutions of MOBS have been estimated from previous measurements with a flowing junction cell. These values of ??E j have been used for correction in order to ascertain the operational pH values of four buffer solutions of MOBS at 25 and 37?°C. These solutions are recommended as pH standards for physiological application in the pH range 7.4 to 7.7. 相似文献
45.
M Collot C Loukou AV Yakovlev CD Wilms D Li A Evrard A Zamaleeva L Bourdieu JF Léger N Ropert J Eilers M Oheim A Feltz JM Mallet 《Journal of the American Chemical Society》2012,134(36):14923-14931
We designed Calcium Rubies, a family of functionalizable BAPTA-based red-fluorescent calcium (Ca(2+)) indicators as new tools for biological Ca(2+) imaging. The specificity of this Ca(2+)-indicator family is its side arm, attached on the ethylene glycol bridge that allows coupling the indicator to various groups while leaving open the possibility of aromatic substitutions on the BAPTA core for tuning the Ca(2+)-binding affinity. Using this possibility we now synthesize and characterize three different CaRubies with affinities between 3 and 22 μM. Their long excitation and emission wavelengths (peaks at 586/604 nm) allow their use in otherwise challenging multicolor experiments, e.g., when combining Ca(2+) uncaging or optogenetic stimulation with Ca(2+) imaging in cells expressing fluorescent proteins. We illustrate this capacity by the detection of Ca(2+) transients evoked by blue light in cultured astrocytes expressing CatCh, a light-sensitive Ca(2+)-translocating channelrhodopsin linked to yellow fluorescent protein. Using time-correlated single-photon counting, we measured fluorescence lifetimes for all CaRubies and demonstrate a 10-fold increase in the average lifetime upon Ca(2+) chelation. Since only the fluorescence quantum yield but not the absorbance of the CaRubies is Ca(2+)-dependent, calibrated two-photon fluorescence excitation measurements of absolute Ca(2+) concentrations are feasible. 相似文献
46.
47.
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
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
48.
Functionalized Graphene as a Gatekeeper for Chiral Molecules: An Alternative Concept for Chiral Separation 下载免费PDF全文
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
49.
One‐Pot Synthesis of O‐Allylhydroxylamines through the Organocatalytic Oxidation of Tertiary Allylic Amines Followed by a [2,3]‐Meisenheimer Rearrangement 下载免费PDF全文
Alexis Theodorou Dr. Dimitris Limnios Prof. Dr. Christoforos G. Kokotos 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):5238-5241
A cheap, green, and highly efficient one‐pot method for the synthesis of O‐protected allylic alcohols is described. By utilizing 2,2,2‐trifluoroacetophenone as the organocatalyst and H2O2 as the oxidant, a variety of allylic amine N‐oxides were synthesized, which upon heating are converted to the final products through a [2,3]‐Meisenheimer rearrangement. 相似文献
50.
We present DFT calculations for adsorption of the first row of transition metal atoms on a MgO(1 0 0) surface and on a surface exhibiting defects. Some atoms exhibit a high adsorption energy on the defect (e.g. Co, Ni and Cu), but others (Ca, Sc) rather adsorb on a clean surface and another set is indifferent to the presence of defect. The adsorption becomes energetically unfavorable when the σ anti-bonding orbitals become populated; this is worse on a defective surface than on a terrace. The π back-donation to the surface contributes to favor the adsorption on the center. 相似文献