全文获取类型
收费全文 | 381篇 |
免费 | 31篇 |
国内免费 | 31篇 |
专业分类
化学 | 203篇 |
晶体学 | 1篇 |
力学 | 10篇 |
数学 | 35篇 |
物理学 | 52篇 |
无线电 | 142篇 |
出版年
2023年 | 8篇 |
2022年 | 13篇 |
2021年 | 17篇 |
2020年 | 10篇 |
2019年 | 8篇 |
2018年 | 6篇 |
2017年 | 12篇 |
2016年 | 10篇 |
2015年 | 11篇 |
2014年 | 18篇 |
2013年 | 13篇 |
2012年 | 25篇 |
2011年 | 29篇 |
2010年 | 15篇 |
2009年 | 30篇 |
2008年 | 32篇 |
2007年 | 31篇 |
2006年 | 31篇 |
2005年 | 18篇 |
2004年 | 20篇 |
2003年 | 7篇 |
2002年 | 19篇 |
2001年 | 6篇 |
2000年 | 9篇 |
1999年 | 10篇 |
1998年 | 2篇 |
1996年 | 8篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1983年 | 1篇 |
排序方式: 共有443条查询结果,搜索用时 11 毫秒
1.
We investigate terahertz radiation(T-rays) from a pentacene organic diode at room temperature. The quantum chemistry calculation for frequency-related Huang–Rhys factor of pentacene is also carried out. The results demonstrate that the T-rays can come from a bending vibration of pentacene skeleton after the energy of pentacene exciton transferring to the vibrational excited state via electron–phonon coupling. Frequency and natural bond orbital analytics of pentacene and its derivatives are performed in order to explain the result and develop new materials to get higher emission. This work provides a new way to produce T-rays with a simple device at room temperature. 相似文献
2.
Due to the salient characteristics such as the time-varying and error-prone wireless links, the dynamic and limited bandwidth, the time-varying traffic pattern and user locations, and the energy constraints, it is a challenging task to efficiently support heterogeneous traffic with different quality of service (CoS) requirements in multihop mobile ad hoc networks. In the last few years, many channel-dependent mechanisms are proposed to address this issue based on the cross-layer design philosophy. However, a lot of problems remain before more efficient solutions are found. One of the problems is how to alleviate the conflict between throughput and fairness for different prioritized traffic, especially how to avoid the bandwidth starvation problem for low-priority traffic when the high-priority traffic load is very high. In this paper, we propose a novel scheme named Courtesy Piggybacking to address this problem. With the recognition of interlayer coupling, our Courtesy Piggybacking scheme exploits the channel dynamics and stochastic traffic features to alleviate the conflict. The basic idea is to let the high-priority traffic help the low-priority traffic by sharing unused residual bandwidth with courtesy. Another noteworthy feature of the proposed scheme is its implementation simplicity: The scheme is easy to implement and is applicable in networks using either reservation-based or contention-based MAC protocols. 相似文献
3.
A capillary electrophoresis (CE) method was developed for the separation of heparin oligosaccharides compatible to study the interactions between the oligosaccharides and granulocyte-colony stimulating factor (G-CSF). Unfractionated heparin was eliminitively degraded to heparin oligosaccharides by an endolytic heparinase. The degraded smaller oligosaccharides (M(r) < 1000) were baseline-separated by CE under a 50 mM phosphate buffer (pH 9.0) in 10 min. Standard heparin disaccharides and larger oligosaccharides (1000 < M(r) < 8000) were all separated under optimized separation conditions. Compared with standard heparin disaccharides, smaller oligosaccharides contained one nonsulfated, two monosulfated, and two disulfated disaccharides, but trisulfated disaccharides were not found. The smaller oligosaccharides were also identified and molecular mass was deduced by electrospray ionization-mass spectrometry (ESI-MS). Furthermore, interactions between G-CSF and the oligosaccharides were studied by using capillary zone electrophoresis (CZE) under the above separation conditions. It was found that larger oligosaccharides could interact with G-CSF while smaller oligosaccharides were not observed to bind to G-CSF under the experimental conditions. In conclusion, the purified heparinase could selectively degrade heparin into oligosaccharides and the interaction between G-CSF and heparin was correlated with the chain length of heparin. 相似文献
4.
Yue Shen Xiaohui Tang Yuwei Xu Haichao Liu Shitong Zhang Bing Yang Yuguang Ma 《中国化学快报》1990,30(11):1947-1950
Cyanophenyl as ancillary acceptor to modify donor-acceptor compound,plays an effective role in shifting the emission color to deep red and maintaining the luminescent efficiency. 相似文献
5.
The self-assembled monolayer structure of the products of elaidic acid iodination (the racemic mixture of 9,10-(9S,10R)-diiodooctadecanoic acid and 9,10-(9R,10S)-diiodooctadecanoic acid) and the products of oleic acid iodination (the racemic mixture of 9,10-(9R,10R)-diiodooctadecanoic acid and 9,10-(9S,10S)-diiodooctadecanoic acid) are studied by high-resolution scanning tunneling microscopy. For the iodination products of elaidic acid, the separation of enantiomers into distinct chiral domains during the formation of the 2-D crystal on the highly ordered pyrolytic graphite (HOPG) surface is not observed. Instead, within the diiodooctadecanoic acid SAM, each row of molecules is composed of opposite racemates. The two opposite racemates pack alternately inside a row, using different faces to adsorb on the surface. The unit cell is composed of a pair of opposite racemates, forming a heterochiral structure. For the iodination products of oleic acid, the racemic mixture is observed to exhibit quasi-phase separation during the formation of the 2-D crystal on the HOPG surface. Each row is composed of homochiral acid molecules, either the 9,10-(9R,10R)-diiodooctadecanoic acid (R) or the 9,10-(9S,10S)-diiodooctadecanoic acid (S). The R row and the S row pack alternately, with a unit cell composed of four molecules. Two of the molecules in the unit cell are the 9,10-(9R,10R)-diiodooctadecanoic acid (R) molecules; two are the 9,10-(9S,10S)-diiodooctadecanoic acid (S) molecules. In the unit cell, the two molecules that have the same chirality pack antiparallel inside the homochiral row, using different faces to adsorb on the surface. These results suggest that several different types of chiral assembly are possible. Enantiomers with opposite chirality exhibit many chiral assembly patterns, forming heterochiral structures on the surface in addition to separation to form macroscopic chiral domains. By using different conformations, similar enantiomers with opposite chirality will display many chiral assembly patterns to form heterochiral structures on the surface. 相似文献
6.
Liu L Qiu S Wang B Zhang W Lu P Xie Z Hanif M Ma Y Shen J 《The journal of physical chemistry. B》2005,109(49):23366-23370
We have investigated the thermal degradation in air by Fourier transform infrared spectroscopy of a ladder-type copolymer containing fluorene units in the backbone (Me-LPF), to reveal the formation of the ketonic defects. As thermal treatment of Me-LPF film at 200 degrees C in air proceeds, a new group of complex absorption bands due to degradation products arises in the range between 1800 and 1600 cm(-1). The observed overlapping bands were separated and assigned by utilizing the second-derivative IR spectral analysis, which can narrow the peak width to one-third of the originals and thereby eases the analysis. The degraded products were assigned as fluorenone (1718 cm(-1)) and benzophenone (Ar-(C=O)-Ar) (1665 cm(-1)), formed by the oxidation of the backbone, and acylphenone (Ar-(C=O)-R) (1685 cm(-1)) from the side chain. The fluorenone was found to be the major component among the degraded products in the main chain, and the time and temperature dependence indicated that the oxidation is a kind of autocatalytic radical-chain process. The oxidation can reach a very high degree (approximately 30% for 6 h oxidation at 240 degrees C estimated by absorption of the alkyl). Our results suggest the possibility of the oxidation of the 9-bialkylfluorene sites. We propose that the degradation of the alkyl in the side chain can help the radicals to propagate in the chain reaction. 相似文献
7.
8.
Yuying Qu Yingchun Li Xiaoli Tan Weixiang Zhai Dr. Guifang Han Dr. Jingli Hou Prof. Guoquan Liu Prof. Yuguang Song Prof. Yangping Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7888-7895
Tetrathiatriarylmethyl (TAM, trityl) radicals have found wide applications as spin probes/labels for EPR spectroscopy and imaging, and as polarizing agents for dynamic nuclear polarization. The high hydrophilicity of TAM radicals is essential for their biomedical applications. However, the synthesis of hydrophilic TAM radicals (e.g., OX063) is extremely challenging and has only been reported in the patent literature, to date. Herein, an efficient synthesis of a highly water-soluble TAM radical bis(8-carboxyl-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d′]bis([1,3]dithiol-4-yl)-mono-(8-carboxyl-2,2,6,6-tetrakis(2-hydroxyethyl)benzo[1,2-d:4,5-d′]bis([1,3]dithiol-4-yl)methyl (TFO), which contains four additional hydroxylethyl groups, relative to the Finland trityl radical CT-03, is reported. Similar to OX063, TFO exhibits excellent properties, including high water solubility in phosphate buffer, low log P, low pKa, long relaxation times, and negligible binding with bovine serum albumin. On the other hand, TFO has a sharper EPR line and higher O2 sensitivity than those of OX063. Therefore, in combination with its facile synthesis, TFO should find wide applications in magnetic resonance related fields and this synthetic approach would shed new light on the synthesis of other hydrophilic TAM radicals. 相似文献
9.
Recyclable 1,2‐bis[3,5‐bis(trifluoromethyl)phenyl]diselane‐catalyzed oxidation of cyclohexene with H2O2: a practical access to trans‐1,2‐cyclohexanediol 下载免费PDF全文
1,2‐Bis[3,5‐bis(trifluoromethyl)phenyl]diselane‐catalyzed oxidation of cyclohexene by hydrogen peroxide affords a quick, clean and practical access to the important compound trans‐1,2‐cyclohexanediol under mild conditions. The highly atom‐economic properties, clean procedures, high reaction concentration, short reaction time, mild conditions and eco‐friendly, recyclable and low loading catalysts facilitate this methodology for possible future practical industrial production. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
10.
Two new silver(I) trans‐cinnamates, namely [Ag(2‐cca)(H2O)]2 ( 1 ) and [Ag(4‐cca)]n ( 2 ) (2‐ccaH = 2‐chlorocinnamic acid and 4‐ccaH = 4‐chlorocinnamic acid), were synthesized and structurally characterized. Single crystal X‐ray studies reveal that each silver(I) atom in 1 is two‐coordinate by a 2‐chlorocinnamate ligand and one water molecule to afford a discrete centrosymmetric dimer with the ligand‐unsupported Ag···Ag interactions (3.218(4) Å), while a pair of symmetry‐related silver(I) atoms in 2 are clamped by two μ2‐η1:η1 4‐chlorocinnamate ligands to yield a binuclear silver(I) moiety incorporating a ligand‐supported Ag···Ag interaction (2.819(5) Å). Both complexes 1 and 2 show potent urease inhibitory activities with the respective IC50 values of 0.66 and 1.10 μM. 相似文献