全文获取类型
收费全文 | 144篇 |
免费 | 0篇 |
国内免费 | 1篇 |
专业分类
化学 | 114篇 |
晶体学 | 1篇 |
力学 | 13篇 |
数学 | 4篇 |
物理学 | 13篇 |
出版年
2024年 | 2篇 |
2023年 | 48篇 |
2022年 | 1篇 |
2021年 | 4篇 |
2020年 | 3篇 |
2019年 | 3篇 |
2018年 | 1篇 |
2017年 | 1篇 |
2015年 | 2篇 |
2014年 | 1篇 |
2013年 | 7篇 |
2012年 | 2篇 |
2011年 | 4篇 |
2010年 | 2篇 |
2009年 | 2篇 |
2008年 | 8篇 |
2007年 | 12篇 |
2006年 | 10篇 |
2005年 | 6篇 |
2004年 | 6篇 |
2003年 | 3篇 |
2002年 | 2篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1987年 | 1篇 |
排序方式: 共有145条查询结果,搜索用时 15 毫秒
1.
The thermal oxidation of an unvulcanized, unstabilized polyisoprene rubber (IR) has been studied in the 40-140 °C temperature range. Ageing was monitored by FTIR determination of double bonds and carbonyl groups, mass uptake measurement, and weight average molar mass determination. A mechanistic scheme based on the standard scheme for radical chain oxidation, but taking into account the diversity of initiation processes and the existence of inter- and intramolecular radical additions to double bonds, was built. The kinetic model derived from this scheme is composed of seven differential equations to be solved in discrete thickness layers to take into account the kinetic control by oxygen diffusion. This system was numerically solved using a Matlab program dedicated to stiff systems of differential equations. The elementary rate constants and other kinetic parameters were then determined from experimental data, using an inverse approach. A set of physically reasonable parameter values was obtained, thus allowing us to envisage lifetime predictions at low temperature (long term). The results led to observations difficult to make from classical analytical studies, for instance the predominance of bimolecular hydroperoxide decomposition among other initiation modes or the competition between intermolecular hydrogen abstraction and intramolecular addition of peroxy radicals to double bonds. 相似文献
2.
F. Gugumus 《Polymer Degradation and Stability》2006,91(9):2079-2092
There are many potential reactions for trans-vinylene groups in oxidizing polyethylene melts. The main possibilities are reactions with peroxy radicals, molecular oxygen, hydroperoxides and peracids. These different reactions can all contribute to the removal of trans-vinylene groups to some extent. This is especially so, for the reactions with hydroperoxides that have been found to be the dominant reactions with vinylidene and vinyl groups in the low temperature range. The reaction with peroxy radicals is thought to be as important relatively as with vinylidene groups. Therefore, the importance of the reaction is decreasing with increasing temperature. However, the most characteristic reaction for trans-vinylene groups can be detected without any doubt only in the advanced stages of processing. It is mechanical stress induced oxygen addition to the double bond. The discussion shows that the reaction should be important from the beginning of processing. The reaction cannot operate with vinyl and vinylidene groups, which are not part of the polyethylene main chain. After oxygen addition to the trans-vinylene group, the “ene” reaction yields an allylic hydroperoxide so that the double bond is not immediately removed. It is acid catalyzed hydroperoxide decomposition that leads to chain scission with aldehyde formation at the new chain ends. 相似文献
3.
The observation data for radon from national geochemical observation points have been collected and analyzed following the Ms 8.0 Wenchuan earthquake on 12th May, 2008 and a post-seismic effect of radon was observed. It has provided the most abundant record since the radon observation network had been set up in china. In this paper, the behaviour of the post-seismic effects of radon gas and water radon is reported. The results were obtained that observation points recording post-seismic effects of radon release were distributed mainly along the extended line of Longmenshan faults, and located on the boundary faults of regional tectonic blocks (Category II) and inside some tectonic blocks (Category II). The pattern of variation in radon emission observed was largely in the form of rising steps. A comparison was made with the variation of water level and flow observed simultaneously with radon measurement, to investigate a dynamic link with post-seismic radon with underground water conditions. This study confirmed a response of radon concentration to the seismic wave, and also raised other scientific issues, such as the dynamic association between geochemical composition of underground water and medium parameter variation of aquifers under dynamic loading, which may support the study of the mechanism of earthquake precursors of radon. 相似文献
4.
Emmanuel Richaud Octavie Okamba Diogo Bruno Fayolle Jacques Verdu Jean Guilment François Fernagut 《Polymer Degradation and Stability》2013
The literature on oxidation kinetics of polyamides and model compounds has been reviewed in order to try to extract suitable information for non-empirical kinetic modeling. Polyamide characteristics are systematically compared to polyolefin ones, these latter being more extensively studied. From kinetic analysis point of view, it is shown that oxidation attacks predominantly α amino methylenes of which C–H bond is considerably weaker than the other methylenes. As a result, propagation by H abstraction is considerably faster in polyamides than in polyethylene for instance. Termination by radical combination is also very fast. Another cause of PA oxidizability is the instability of α amino hydroperoxides linked to the inductive effect of nitrogen. This instability is responsible for many key features of oxidation kinetics especially the absence of induction period. 相似文献
5.
F. Gugumus 《Polymer Degradation and Stability》2006,91(12):3416-3428
Aldehydes and acids can be formed in numerous reactions in oxidizing polyethylene melts. Significant amounts of aldehydes result from β-scission of alkoxy radicals that are formed on bimolecular hydroperoxide decomposition. There are also large amounts of aldehydes expected from acid-catalyzed decomposition of allylic hydroperoxides as soon as enough acids have accumulated for efficient catalysis. There are difficulties in explaining the formation of aldehydes at a constant rate in sufficient amount for explaining the experimental data. There are much less difficulties with the constant rate of carboxylic acid formation. The α,γ-keto-hydroperoxides that are formed on chain propagation might account for the bulk of the acids formed at a constant rate.The foremost problems with the acids pertain to their formation at increasing rates in the initial as well as in the advanced stages. Formation and decomposition of α,β-di-hydroperoxides and α,γ-di-hydroperoxides is a possibility in this respect. Similarly, α,β-keto-hydroperoxides might be formed on peroxidation in the α-position to ketone groups in the advanced stages. There are considerable difficulties in elucidating the exact role of the aldehydes that are usually seen as the main precursors of the acids. Although there are many possibilities for transformation of aldehydes into acids, the free radical mechanisms envisaged usually have considerable disadvantages. These disadvantages result essentially from fast decarbonylation of acyl radicals and even faster decarboxylation of acyl-oxy radicals. Direct transformation of peracids into acids on reaction with double bonds is always a possibility. Moreover, in the low temperature range (150-160 °C) where hydroperoxides are accumulating, direct reaction of aldehydes with primary and/or secondary hydroperoxides will also yield acids. 相似文献
6.
Gavin O. Jones 《Tetrahedron》2019,75(14):2047-2055
Quantum chemistry has increasingly become an integral component for the development of homogeneous catalytic processes to form polymers and to break them down. This review examines how quantum chemistry has been utilized to gain insights on mechanisms and selectivities in polymerization and depolymerization reactions by homogeneous catalysts, from some of the earliest uses of theory to the most recent efforts. Key aspects of catalysis by transition-metal catalysts, organocatalytic bases and organic acids will be highlighted. 相似文献
7.
Dr. Kazuto Suzuki Dr. Joshua Kyle Stanfield Dr. Keita Omura Dr. Yuma Shisaka Dr. Shinya Ariyasu Chie Kasai Dr. Yuichiro Aiba Dr. Hiroshi Sugimoto Prof. Dr. Osami Shoji 《Angewandte Chemie (International ed. in English)》2023,62(13):e202215706
Catching the structure of cytochrome P450 enzymes in flagrante is crucial for the development of P450 biocatalysts, as most structures collected are found trapped in a precatalytic conformation. At the heart of P450 catalysis lies Cpd I, a short-lived, highly reactive intermediate, whose recalcitrant nature has thwarted most attempts at capturing catalytically relevant poses of P450s. We report the crystal structure of P450BM3 mimicking the state in the precise moment preceding epoxidation, which is in perfect agreement with the experimentally observed stereoselectivity. This structure was attained by incorporation of the stable Cpd I mimic oxomolybdenum mesoporphyrin IX into P450BM3 in the presence of styrene. The orientation of styrene to the Mo-oxo species in the crystal structures sheds light onto the dynamics involved in the rotation of styrene to present its vinyl group to Cpd I. This method serves as a powerful tool for predicting and modelling the stereoselectivity of P450 reactions. 相似文献
8.
F. Gugumus 《Polymer Degradation and Stability》2006,91(6):1346-1355
Most products formed on polyethylene oxidation result from hydroperoxide decomposition. The product yields can be calculated for various mechanisms of hydroperoxide decomposition. This work concerns the reaction of a hydroperoxide with an alcohol group thought to be dominant in the advanced stages of polyethylene processing in the high temperature range (170-200 °C). Besides hydrogen abstraction by caged alkoxy radicals already envisaged previously, the possibility of β-scission is taken into account. This additional reaction introduces significant complexity into the reaction schemes. This is especially so because additional caged radical pairs must be included into the schemes and the calculations. It becomes possible to calculate the yields of aldehyde and vinyl groups that do not result from hydroperoxide decomposition in the absence of β-scission. The yields of the main oxidation products such as alcohols and ketones are not much affected by taking into account β-scission. The yield of aldehydes is important in the whole temperature range and increases considerably if the temperature is raised from 170 to 200 °C. It becomes more important than the ketone yield. The vinyl groups are formed in amounts corresponding roughly to 10-15% of the trans-vinylene groups in the temperature range of 170-200 °C. 相似文献
9.
CVD法不同条件下制备的多壁碳纳米管的Fenton氧化改性 总被引:2,自引:0,他引:2
碳纳米管经焙烧和稀硝酸纯化处理后,在相同的实验条件下,采用Fenton试剂产生的·OH分别对CVD法合成的两种制备条件不同的多壁碳纳米管进行氧化改性处理。红外光谱(FT IR)表明,改性后的两种碳管结构中都引入了羟基、羰基和羧基等含氧官能团。此外,由于制备条件不同,导致它们的石墨化程度、缺陷含量和抗氧化能力等性质也不同,因此CVD法制备条件能够对碳管Fenton氧化改性结果产生重要影响。机理分析表明,这些含氧官能团可以看作是具有强亲电性和强氧化性的·OH对碳管上缺陷位置和不饱和键进行攻击的结果。 相似文献
10.
Transition structures associated with the C-C bond-formation step of the proline-catalyzed intermolecular aldol reaction
between acetone and isobutyraldehyde have been studies using density functional theory methods at the B3LYP/6-31G** computational
level. A continuum model has been selected to represent solvent effects. For this step, which is the stereocontrolling and
rate-determining step, four reactive channels corresponding to the syn and anti arrangement of the active methylene of the
enamine relative to the carboxylic acid group of l-proline and the re and si attack modes to both faces of the aldehyde carbonyl group have been analyzed. The B3LYP/6-31G**
energies are in good agreement with experiment, allowing us to explain the origin of the catalysis and stereoselectivity for
these proline-catalyzed aldol reactions.
Received: 2 April 2002 / Accepted: 18 July 2002 / Published online: 11 October 2002
Acknowledgements. This work was supported by research funds provided by the Ministerio de Educación y Cultura of the Spanish Government by
DGICYT (project PB98–1429). All the calculations were performed on a Cray–Silicon Graphics Origin 2000 of the Servicio de
Informática de la Universidad de Valencia. We are most indebted to this center for providing us with computer capabilities.
Correspondence to: L. R. Domingo e-mail: domingo@utopia.uv.es 相似文献