全文获取类型
收费全文 | 322篇 |
免费 | 18篇 |
国内免费 | 1篇 |
专业分类
化学 | 191篇 |
力学 | 6篇 |
数学 | 15篇 |
物理学 | 70篇 |
无线电 | 59篇 |
出版年
2023年 | 6篇 |
2022年 | 3篇 |
2021年 | 6篇 |
2020年 | 8篇 |
2019年 | 7篇 |
2018年 | 6篇 |
2017年 | 6篇 |
2016年 | 3篇 |
2015年 | 5篇 |
2014年 | 11篇 |
2013年 | 39篇 |
2012年 | 15篇 |
2011年 | 18篇 |
2010年 | 10篇 |
2009年 | 12篇 |
2008年 | 16篇 |
2007年 | 19篇 |
2006年 | 20篇 |
2005年 | 16篇 |
2004年 | 8篇 |
2003年 | 5篇 |
2002年 | 3篇 |
2001年 | 6篇 |
2000年 | 7篇 |
1999年 | 7篇 |
1998年 | 5篇 |
1997年 | 9篇 |
1996年 | 6篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 6篇 |
1991年 | 1篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 4篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 1篇 |
1980年 | 2篇 |
1979年 | 6篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1973年 | 3篇 |
1968年 | 2篇 |
1943年 | 1篇 |
1940年 | 1篇 |
排序方式: 共有341条查询结果,搜索用时 0 毫秒
11.
The bimolecular rate constant of k (9.4 ± 2.4 × 10?12 cm3 molecule?1 s?1 was measured using the relative rate technique for the reaction of the nitrate radical (NO3?) with 4‐(2,6,6‐trimethyl‐1‐cyclohexen‐1‐yl)‐3‐buten‐2‐one (β‐ionone) at (297 ± 3) K and 1 atmosphere total pressure. In addition, the products of β‐ionone + NO3? reaction were also investigated. The identified reaction products were glyoxal (HC(?O)C(?O)H), and methylglyoxal (CH3C(?O)C(?O)H). Derivatizing agents O‐(2,3,4,5,6‐pentafluorobenzyl)hydroxylamine and N,O‐bis(trimethylsilyl)trifluoroacetamide were used to propose the other major reaction products: 3‐oxobutane‐1,2‐diyl nitrate, 2,6,6‐trimethylcyclohex‐1‐ene‐carbaldehyde, 2‐oxo‐1‐(2,6,6‐trimethylcyclohex‐1‐en‐1‐yl)ethyl nitrate, pentane‐2,4‐dione, 3‐oxo‐1‐(2,6,6‐trimethylcyclohex‐1‐en‐1‐yl)butane‐1,2‐diyl dinitrate, 3,3‐dimethylcyclohexane‐1,2‐dione, and 4‐oxopent‐2‐enal. The elucidation of these products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible β‐ionone + NO3? reaction mechanisms based on previously published volatile organic compound + NO3? gas‐phase mechanisms. The additional gas‐phase products 5‐acetyl‐2‐ethylidene‐3‐methylcyclopentyl nitrate, 1‐(1‐hydroxy‐7,7‐dimethyl‐2,3,4,5,6,7‐hexahydro‐1 H‐inden‐2‐yl)ethanone, 1‐(1‐hydroxy‐3a,7‐dimethyl‐2,3,3a,4,5,6,‐hexahydro‐1 H‐inden‐2‐yl)ethanone, and 5‐acetyl‐2‐ethylidene‐3‐methylcyclopentanone are proposed to be the result of cyclization through a reaction intermediate. © 2009 Wiley Periodicals, Inc. * 1 This article is a U.S. Government work and, as such, is in the public domain of the United States of America. Int J Chem Kinet 41: 629–641, 2009 相似文献
12.
13.
Alex van der Ham Thomas Hansen Dr. Gerrit Lodder Dr. Jeroen D. C. Codée Dr. Trevor A. Hamlin Dr. Dmitri V. Filippov 《Chemphyschem》2019,20(16):2103-2109
Lithium ion selective crown ethers have been the subject of much research for a multitude of applications. Current research is aimed at structurally rigidifying crown ethers, as restructuring of the crown ether ring upon ion binding is energetically unfavorable. In this work, the lithium ion binding ability of the relatively rigid 8-crown-4 was investigated both computationally by density functional theory calculations and experimentally by 1H and 7Li NMR spectroscopy. Although both computational and experimental results showed 8-crown-4 to bind lithium ion, this binding was found to be weak compared to larger crown ethers. The computational analysis revealed that the complexation is driven by enthalpy rather than entropy, illustrating that rigidity is only of nominal importance. To elucidate the origin of the favorable interaction of lithium ion with crown ethers, activation strain analyses and energy decomposition analyses were performed pointing to the favorable interaction being mainly electrostatic in nature. 8-crown-4 presents the smallest crown ether reported to date capable of binding lithium ion, possessing two distinct conformations from which it is able to do so. 相似文献
14.
Won Seok Ham Julius Hillenbrand Jrme Jacq Christophe Genicot Tobias Ritter 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(2):542-546
(Hetero)arylamines constitute some of the most prevalent functional molecules, especially as pharmaceuticals. However, structurally complex aromatics currently cannot be converted into arylamines, so instead, each product isomer must be assembled through a multistep synthesis from simpler building blocks. Herein, we describe a late‐stage aryl C?H amination reaction for the synthesis of complex primary arylamines that other reactions cannot access directly. We show and rationalize through a mechanistic analysis the reasons for the wide substrate scope and the constitutional diversity of the reaction, which gives access to molecules that would not have been readily available otherwise. 相似文献
15.
16.
We report the spontaneous dimerization process of the full-length Aβ42 proteins in water by using unguided, fully atomistic, explicit-water molecular dynamics simulations. Based on the thermodynamic analysis, we demonstrate that Aβ42 dimerization in water occurs via a two-step nucleation-accommodation mechanism driven by water-induced force and by protein internal force, respectively. 相似文献
17.
Jungyeob Ham 《Tetrahedron letters》2005,46(39):6683-6686
A new synthesis of an agonist for the peroxisome proliferator-activated receptor δ (PPARδ) GW501516 as a potential antiobesity drug is described. The synthetic route involves the in situ protection of the phenol group with a Grignard reagent and a regio-controlled one-pot reaction for the formation of a sulfide bond as the key step. Starting from commercially available 4-iodo-2-methylphenol, this approach affords GW501516 with an overall yield of 87%. 相似文献
18.
Determination of rimantadine in pharmaceutical preparations by capillary zone electrophoresis with indirect detection or after derivatization 总被引:2,自引:0,他引:2
Summary Rimantadine is synthetic analog of amantadine; both are antiviral agents used for prophylaxis and treatment of influenza A.
A capillary zone electrophoretic (CZE) procedure for the determination of rimantadine has been developed. As the direct determination
of rimantadine is poorly sensitive because the compound is almost transparent in the UV/Vis range, several indirect methods
were studied. Two were found to be the particularly useful: (a) indirect detection using 5 mM 4-methylbenzylamine in 1:4 methanol-water
as absorbing background electrolyte, with detection at 210 nm, and (b) derivatization of rimantadine with 1,2-naphthoquinone-4-sulfonic
acid in alkaline medium and subsequent determination of the derivative by CZE (40 mM tetraborate, pH 9.2, detection at 280
nm). Uncoated capillary tubing, 44 cm length ×75 μM i.d., was used for both determinations. The detection limits were 0.1
and 2 ppm for methods a and b, respectively. The methods were used to determine rimantadine in pharmaceutical products and
for dissolution testing of Flumadin? tablets. 相似文献
19.
George E. Ham 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(2):227-230
It is shown that for the reported instances of “random” copolymerization in cationic systems, N values related to relative reactivity may be derived for monomers. The N values approximate reasonably well the values of the function, exp (-e) - 1.23, where e is the polarity e of the Q-e scheme for free-radical copolymerizations.
In a recent paper [1] it was shown that for the reported instances [2-4] of “random” copolymerization (r1,r2 = 1) in cationic systems, N values, related to relative reactivity, might be derived for monomers, employing styrene as a base monomer (N = 1). Thus d[M1]/d[M2] =N1[M1]/N2[M2] (1)
where d[M1]/d[M2] is the instantaneous copolymer composition, [M1]/[M2] is the ratio of unreacted monomers, and N1 and N2 are parameters related to general monomer reactivity of monomers 1 and 2, respectively, in cationic copolymerization. 相似文献
20.
Tian Jin Lu Zhao Maolin Huang Yan Yue Zhe-Bin Zheng Won-Hun Ham 《Tetrahedron: Asymmetry》2017,28(5):725-729
Concise stereoselective syntheses of (?)-clavaminol A and deacetyl (+)-clavaminol H have been achieved from simple starting materials. Highlights of the synthesis for (?)-clavaminol A include a highly diastereoselective chelation-controlled hydride reduction of an amino ketone to give the anti amino alcohol directly, and NaBH4-mediated dehalogenation. The main synthetic approach for deacetyl (+)-clavaminol H features a highly diastereoselective chelation-controlled hydride reduction of the amino ketone to construct the anti amino alcohol and a palladium catalyzed hydrogenation reaction at the final step. 相似文献