全文获取类型
收费全文 | 383篇 |
免费 | 21篇 |
国内免费 | 18篇 |
专业分类
化学 | 325篇 |
晶体学 | 2篇 |
力学 | 3篇 |
数学 | 15篇 |
物理学 | 77篇 |
出版年
2024年 | 1篇 |
2023年 | 2篇 |
2022年 | 4篇 |
2021年 | 8篇 |
2020年 | 11篇 |
2019年 | 10篇 |
2018年 | 9篇 |
2017年 | 10篇 |
2016年 | 13篇 |
2015年 | 6篇 |
2014年 | 14篇 |
2013年 | 13篇 |
2012年 | 20篇 |
2011年 | 24篇 |
2010年 | 11篇 |
2009年 | 16篇 |
2008年 | 22篇 |
2007年 | 18篇 |
2006年 | 33篇 |
2005年 | 23篇 |
2004年 | 17篇 |
2003年 | 20篇 |
2002年 | 21篇 |
2001年 | 20篇 |
2000年 | 11篇 |
1999年 | 4篇 |
1998年 | 1篇 |
1997年 | 7篇 |
1996年 | 9篇 |
1995年 | 8篇 |
1994年 | 5篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1985年 | 1篇 |
1982年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 4篇 |
1970年 | 1篇 |
1939年 | 2篇 |
排序方式: 共有422条查询结果,搜索用时 0 毫秒
1.
The spin coating method was used to assemble polymer (Poly (2,5-dibutoxy-1,4-phenylenevinylene)) (DBO-PPV) into the pores of porous alumina which was prepared by anodization. Four peaks in the photoluminescence (PL) spectra of the composite, with contributions from the DBO-PPV and porous alumina, were found. It was also found that the light emitting from the porous alumina could excite the photoluminescence of DBO-PPV. The nanometer effect of the porous alumina can lead to a blue shift of 90 nm of the PL peaks of DBO-PPV. 相似文献
2.
Katalytische Epoxidierung und 1,2‐Dihydroxylierung von Olefinen mit Bispidin‐Eisen(II)/H2O2‐Systemen
3.
Bassan A Blomberg MR Siegbahn PE Que L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):692-705
The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane. 相似文献
4.
通过镁离子内扩散铌酸锂单晶光纤,以改变晶纤表层的折射率,首次在国内实现了沿不同轴向生长、不同掺杂的铌酸锂单晶光纤的芯-包层波导结构。通过匹配扩散温度、扩散时间、MgO膜厚等扩散参数及选择合适的晶纤直径,实现了晶纤具有阶跃和抛物折射率分布的包层,并对包层晶纤的模式特性进行了观察,得到低次模传输。 相似文献
5.
Rashid MA Gustafson KR Crouch RC Groweiss A Pannell LK Van QN Boyd MR 《Organic letters》2002,4(19):3293-3296
Poecillastrin A (1), a new polyketide-derived macrolide lactam, was isolated from a deep-water collection of the marine sponge Poecillastra species. The structure of poecillastrin A (1) was assigned using NMR data acquired at 500 MHz with an inverse-detection cryogenic probe and at 800 MHz with a room-temperature probe. 相似文献
6.
Kryatov SV Chavez FA Reynolds AM Rybak-Akimova EV Que L Tolman WB 《Inorganic chemistry》2004,43(6):2141-2150
Dioxygen activation by enzymes such as methane monooxygenase, ribonucleotide reductase, and fatty acid desaturases occurs at a nonheme diiron active site supported by two histidines and four carboxylates, typically involving a (peroxo)diiron(III,III) intermediate in an early step of the catalytic cycle. Biomimetic tetracarboxylatodiiron(II,II) complexes with the familiar "paddlewheel" topology comprising sterically bulky o-dixylylbenzoate ligands with pyridine, 1-methylimidazole, or THF at apical sites readily react with O(2) to afford thermally labile peroxo intermediates that can be trapped and characterized spectroscopically at low temperatures (193 K). Cryogenic stopped-flow kinetic analysis of O(2) adduct formation carried out for the three complexes reveals that dioxygen binds to the diiron(II,II) center with concentration dependences and activation parameters indicative of a direct associative pathway. The pyridine and 1-methylimidazole intermediates decay by self-decomposition. However, the THF intermediate decays much faster by oxygen transfer to added PPh(3), the kinetics of which has been studied with double mixing experiments in a cryogenic stopped-flow apparatus. The results show that the decay of the THF intermediate is kinetically controlled by the dissociation of a THF ligand, a conclusion supported by the observation of saturation kinetic behavior with respect to PPh(3), inhibition by added THF, and invariant saturation rate constants for the oxidation of various phosphines. It is proposed that the proximity of the reducing substrate to the peroxide ligand on the diiron coordination sphere facilitates the oxygen-atom transfer. This unique investigation of the reaction of an O(2) adduct of a biomimetic tetracarboxylatodiiron(II,II) complex provides a synthetic precedent for understanding the electrophilic reactivity of like adducts in the active sties of nonheme diiron enzymes. 相似文献
7.
W. Palmaer E. Heyn O. Bauer H. E. Searle F. L. La Que W. R. van Wijk H. J. Lodeesen Nathalie Goldowski H. Fournier H. Thyssen J. Bourdouxhe E. Naumann U. R. Evans und W. Blum 《Fresenius' Journal of Analytical Chemistry》1939,116(5-6):216-221
Ohne Zusammenfassung 相似文献
8.
A family of modified two-derivative Runge–Kutta (MTDRK) methods for the integration of the Schrödinger equation are obtained. Two new three-stage and fifth order TDRK methods are derived. The numerical results in the integration of the radial Schrödinger equation with the Woods–Saxon potential are reported to show the high efficiency of our new methods. The results of the error analysis are illustrated by the resonance problem. 相似文献
9.
10.
Jie Feng Yonglei Chen Yangxia Han Juanjuan Liu Cuiling Ren Xingguo Chen 《Analytica chimica acta》2016
In recent years, extensive researches are focused on the fluorescent carbon nanoparticles (CNPs) due to their excellent photochemical, biocompatible and water-soluble properties. However, these synthesis methods are generally suffered from tedious processes. In this paper, fluorescent carbon nanoparticles are synthesized by a facile, one-pot, low-temperature method with trypsin and dopamine as precursors. The synthesis process avoids any heating operation and organic solvent, which provides a “green” and effective preparation route. The obtained CNPs exhibit excellent water-solubility, salt-tolerance and photostability. Based on the synergistic action of the inner filter effect and static quenching mechanism, the CNPs are exploited as a “turn-off” fluorescence sensor for sensitive and selective detection of Fe3+ ions. The probe shows a wide linear range from 0.1 to 500 μM, with a limit of detection of 30 nM. Furthermore, the as-fabricated fluorescent sensing system is successfully applied to the analysis of Fe3+ in biological samples such as human urine and serum samples with satisfactory recoveries (92.8–113.3%). 相似文献