全文获取类型
收费全文 | 734篇 |
免费 | 38篇 |
国内免费 | 3篇 |
专业分类
化学 | 656篇 |
力学 | 2篇 |
数学 | 79篇 |
物理学 | 38篇 |
出版年
2023年 | 2篇 |
2022年 | 2篇 |
2021年 | 7篇 |
2020年 | 9篇 |
2019年 | 9篇 |
2018年 | 3篇 |
2017年 | 5篇 |
2016年 | 21篇 |
2015年 | 20篇 |
2014年 | 25篇 |
2013年 | 40篇 |
2012年 | 59篇 |
2011年 | 65篇 |
2010年 | 37篇 |
2009年 | 32篇 |
2008年 | 74篇 |
2007年 | 66篇 |
2006年 | 58篇 |
2005年 | 44篇 |
2004年 | 52篇 |
2003年 | 36篇 |
2002年 | 28篇 |
2001年 | 6篇 |
2000年 | 13篇 |
1999年 | 3篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1996年 | 9篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1993年 | 7篇 |
1991年 | 5篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有775条查询结果,搜索用时 31 毫秒
51.
This study describes the optimisation of an analytical method to determine 54 volatile organic compounds (VOCs) in air samples by active collection on multisorbent tubes, followed by thermal desorption and gas chromatography-mass spectrometry. Two multisorbent beds, Carbograph 1/Carboxen 1000 and Tenax/Carbograph 1TD, were tested. The latter gave better results, mainly in terms of the peaks that appeared in blank chromatograms. Temperatures, times and flow desorption were optimised. Recoveries were higher than 98.9%, except methylene dichloride, for which the recovery was 74.9%. The method's detection limits were between 0.01 and 1.25 μg m−3 for a volume sample of 1200 ml, and the repeatability on analysis of 100 ng of VOCs, expressed as relative standard deviation for n = 3, was lower than 4% for all compounds. Urban and industrial air samples from the Tarragona region were analysed. Benzene, toluene, ethylbenzene and xylenes (BTEX) were found to be the most abundant VOCs in urban air. Total VOCs in urban samples ranged between 18 and 307 μg m−3. Methylene chloride, 1,4-dichlorobenzene, chloroform and styrene were the most abundant VOCs in industrial samples, and total VOCs ranged between 19 and 85 μg m−3. 相似文献
52.
53.
54.
Properties of In situ polymerized poly(3,4‐ethylenedioxythiophene)/alumina composites for energy storage applications
下载免费PDF全文
![点击此处可从《Journal of Polymer Science.Polymer Physics》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Mari Cruz G. Saborío Francesc Estrany Carlos Alemán 《Journal of Polymer Science.Polymer Physics》2017,55(15):1131-1141
Composites formed by poly(3,4‐ethylenedioxythiophene) and alumina (PEDOT/Al2O3) have been prepared by in situ anodic polymerization. For this purpose, the stability of 1:1 and 4:1 monomer:alumina aqueous solutions has been examined as a function of the pH (2.3, 4.0, 7.0, 8.8, or 10.8). Results indicate that the monomer behaves as a dispersant that remains stable at the studied basic pHs despite they are close to the isoelectric point of alumina. Although the thermal stability of the composites is considerably affected by the pH of the reaction medium, its influence on the surface morphology is very small. Independently, of the synthetic conditions, the electrochemical properties were better for PEDOT/Al2O3 than for pure PEDOT, reflecting that alumina particles promote the charge mobility. The highest specific capacitance (SC; 141 F/g), which was 55% higher than that obtained for pure PEDOT, was achieved for the composite prepared at pH = 8.8 using a 4:1 monomer:alumina ratio. These conditions favor the participation of OH– groups as secondary doping agents without degrading the polymer matrix and enhance the specific surface of the films, facilitating the ionic mobility. On the other hand, application of a multi‐step polymerization strategy has shown that interfaces originated by consecutive steps enhance the SC. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1131–1141 相似文献
55.
56.
We show that a tangle of light superconducting strings in the Milky Way could be the source of the observed 511 keV emission from electron-positron annihilation in the Galactic bulge. The scenario predicts a flux that is in agreement with observations if the strings are at the approximately 1 TeV scale, making the particle physics within reach of planned accelerator experiments. The emission is directly proportional to the galactic magnetic field, and future observations should be able to differentiate the superconducting string scenario from other proposals. 相似文献
57.
The present study describes an extensive conformational search of substance P using two different computational methods. On the one hand, the peptide was studied using the iterative simulated annealing, and on the other, molecular dynamics simulations at 300 and 400 K. With the former method, the peptide was studied in vacuo with a dielectric constant of 80, whereas using the latter study the peptide was studied in a box of TIP3P water molecules. Analysis of the results obtained using both methodologies was carried out using an in-house methodology using a cluster analysis method based on information theory. Comparison of the two sampling methodologies and the different environment used in the calculations is also analyzed. Finally, the conformational motifs that are characteristic of substance P in a hydrophilic environment are presented and compared with the experimental results available in the literature. 相似文献
58.
Racemic and enantiopure ((p)()S)-1-bromo-2-methylferrocene 6 were synthesized in 4 steps from 2-(4,4-dimethyloxazolinyl)ferrocene and (S)-2-(4-methylethyloxazolinyl)ferrocene, respectively (46 and 81% overall yield). Bromolithium exchange and addition of ClPR(2) gave the corresponding racemic or enantiopure 2-methylferrocenyl phosphine ligands 2-MeFcPR(2) 11 (R = Ph), 12 (R = Cy), and 13 (R = (t)Bu) in 28-93% yield. Use of PCl(3) gave the C(3)-symmetric phosphine (2-MeFc)(3)P 5 from ((p)()S)-6(72% yield) but racemic 6 did not lead to the formation of triferrocenyl phosphines. Combination of 5 and Pd(2)(dba)(3) gave an active catalyst for the Suzuki reaction of aryl chlorides, for example, 4-chlorotoluene and phenylboronic acid reacted at only 60 degrees C in dioxane (86% yield). Other examples are reported together with the use of 12 in this same protocol. From the X-ray crystal structure of 5 the cone angle was determined as 211 degrees. With this, and the electronic character of 11, 12, and other phosphines (derived from nu(CO) of trans-[(R(3)P)(2)Rh(CO)Cl]), an analysis is made of the steric and electronic influences on ligand activity in the Suzuki reaction. 相似文献
59.
Tutusaus O Viñas C Kivekäs R Sillanpää R Teixidor F 《Chemical communications (Cambridge, England)》2003,(19):2458-2459
Designed ligands have been synthesised to produce the first arene-like metallacarborane. For arene-like coordination the number of electronegative elements on the coordinating site must be kept to a minimum. Choosing ligands with bulky substituents on the heteroatom allows easy rearrangement and arene-like coordination. This is more hampered the higher the number of hetereoatoms to be re-located. 相似文献
60.