全文获取类型
收费全文 | 528篇 |
免费 | 20篇 |
国内免费 | 1篇 |
专业分类
化学 | 344篇 |
晶体学 | 4篇 |
力学 | 23篇 |
数学 | 81篇 |
物理学 | 97篇 |
出版年
2023年 | 3篇 |
2022年 | 2篇 |
2021年 | 3篇 |
2020年 | 3篇 |
2019年 | 7篇 |
2018年 | 12篇 |
2017年 | 4篇 |
2016年 | 25篇 |
2015年 | 17篇 |
2014年 | 19篇 |
2013年 | 33篇 |
2012年 | 47篇 |
2011年 | 61篇 |
2010年 | 35篇 |
2009年 | 18篇 |
2008年 | 43篇 |
2007年 | 33篇 |
2006年 | 34篇 |
2005年 | 27篇 |
2004年 | 23篇 |
2003年 | 22篇 |
2002年 | 17篇 |
2001年 | 7篇 |
2000年 | 7篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1996年 | 4篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 7篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1978年 | 4篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有549条查询结果,搜索用时 31 毫秒
1.
Olivier Herbinet Benoit Husson Hervé Le Gall Frédérique Battin-Leclerc 《国际化学动力学杂志》2020,52(12):1006-1021
In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high-pressure jet-stirred reactor for the oxidation of three molecules, which are considered in surrogates of diesel fuel, n-heptane, ethylbenzene, and n-butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from 500 to 1 100 K, and for a residence time of 2 s. Based on results previously obtained close to the atmospheric pressure for the same molecules, the pressure effect on fuel conversion and product selectivity was discussed. In addition, for the three fuels, the experimental temperature dependence of species mole fractions was compared with simulations using recent literature models with generally a good agreement. For n-heptane, the obtained experimental data, at 10 bar for stoichiometric mixtures, included the temperature dependence of the mole fractions of the reactants and those of 21 products. Interestingly, the formation of species previously identified as C7 diones was found significantly enhanced at 10 bar compared with lower pressures. The oxidation of ethyl- and n-butylbenzenes was investigated at 10 bar for equivalence ratios of 0.5, 1, and 2. The obtained experimental data included the temperature dependence of the mole fractions of the reactants and those of 13 products for the C8 fuels and of 19 products for the C10 one. For ethylbenzene under stoichiometric conditions, the pressure dependence (from 1 to 10 bar) of species mole fraction was also recorded and compared with simulations with more deviations obtained than for temperature dependence. For both aromatic reactants, a flow rate analysis was used to discuss the main pressure influence on product selectivities. 相似文献
2.
Antoine Bardin Pierre-Yves Le Gac Hervé Bindi Bruno Fayolle 《Journal of polymer science. Part A, Polymer chemistry》2020,58(22):3170-3182
This publication highlights the structure–property relationships in several thermoplastic elastomers (TPEs): one poly(ether-block-amide) and two thermoplastic polyurethane elastomers with ester and ether soft blocks. Structural changes are induced by chemical degradation from virgin samples through hydrolysis and oxidation. Molar mass measurements show an exclusive chain scission mechanism for all TPEs, regardless of the chemical modification condition. Mechanical behavior was nevertheless obtained from uniaxial tensile testing and fracture testing while considering the essential work of fracture (EWF) concept. During the macromolecular scission process, elongation at break shows a plateau followed by a drop, while stress at break decreases steadily. Once again, the trend is identical for all TPEs in all conditions considered. The βwp parameter determined using the EWF concept exhibits an interesting sensitivity to scissions (i.e., molar mas decrease). Plotting elongation at break as a function of molar mass reveals a strong correlation between these two parameters. This master curve is particularly remarkable considering the range of TPEs and chemical breakdown pathways considered (hydrolysis and oxidation at several temperatures). Relevant structure–property relationships are proposed, highlighting that molar mass is a predominant parameter for determining the mechanical properties of thermoplastic elastomers. 相似文献
3.
The generation of air microbubbles in microfluidic systems or in capillaries could be of great interest for transportation (single cell analysis, organite transportation) or for liquid compartmentation. The physicochemical characterization of air bubbles and a better understanding of the process leading to bubble generation during electrophoresis is also interesting in a theoretical point of view. In this work, the generation of microbubbles on hydrophobic Glaco™ coated capillaries has been studied in water-based electrolyte. Air bubbles were generated at the detection window and the required experimental parameters for microbubbles generation have been identified. Generated bubbles migrated against the electroosmotic flow, as would do strongly negatively charged solutes, under constant electric field. They have been characterized in terms of dimensions, electrophoretic mobility, and apparent charge. 相似文献
4.
Macrocyclic Gd3+ Complexes with Pendant Crown Ethers Designed for Binding Zwitterionic Neurotransmitters 下载免费PDF全文
Dr. Fatima Oukhatar Hervé Meudal Dr. Céline Landon Prof. Dr. Nikos K. Logothetis Prof. Dr. Carlos Platas‐Iglesias Priv.‐Doz. Dr. Goran Angelovski Dr. Éva Tóth 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11226-11237
A series of Gd3+ complexes exhibiting a relaxometric response to zwitterionic amino acid neurotransmitters was synthesized. The design concept involves ditopic interactions 1) between a positively charged and coordinatively unsaturated Gd3+ chelate and the carboxylate group of the neurotransmitters and 2) between an azacrown ether appended to the chelate and the amino group of the neurotransmitters. The chelates differ in the nature and length of the linker connecting the cyclen‐type macrocycle that binds the Ln3+ ion and the crown ether. The complexes are monohydrated, but they exhibit high proton relaxivities (up to 7.7 mM ?1 s?1 at 60 MHz, 310 K) due to slow molecular tumbling. The formation of ternary complexes with neurotransmitters was monitored by 1H relaxometric titrations of the Gd3+ complexes and by luminescence measurements on the Eu3+ and Tb3+ analogues at pH 7.4. The remarkable relaxivity decrease (≈80 %) observed on neurotransmitter binding is related to the decrease in the hydration number, as evidenced by luminescence lifetime measurements on the Eu3+ complexes. These complexes show affinity for amino acid neurotransmitters in the millimolar range, which can be suited to imaging concentrations of synaptically released neurotransmitters. They display good selectivity over non‐amino acid neurotransmitters (acetylcholine, serotonin, and noradrenaline) and hydrogenphosphate, but selectivity over hydrogencarbonate was not achieved. 相似文献
5.
Insights into the Catalytic Activity of Nitridated Fibrous Silica (KCC‐1) Nanocatalysts from 15N and 29Si NMR Spectroscopy Enhanced by Dynamic Nuclear Polarization 下载免费PDF全文
Dr. Aany Sofia Lilly Thankamony Dr. Cédric Lion Dr. Frédérique Pourpoint Baljeet Singh Dr. Angel J. Perez Linde Dr. Diego Carnevale Prof. Geoffrey Bodenhausen Dr. Hervé Vezin Prof. Olivier Lafon Prof. Vivek Polshettiwar 《Angewandte Chemie (International ed. in English)》2015,54(7):2190-2193
Fibrous nanosilica (KCC‐1) oxynitrides are promising solid‐base catalysts. Paradoxically, when their nitrogen content increases, their catalytic activity decreases. This counterintuitive observation is explained here for the first time using 15N‐solid‐state NMR spectroscopy enhanced by dynamic nuclear polarization. 相似文献
6.
7.
[2+1] Cycloaddition Affording Methylene‐ and Vinylidenecyclopropane Derivatives: A Journey around the Reactivity of Metal‐Phosphinito–Phosphinous Acid Complexes 下载免费PDF全文
Metal–phosphinito–phosphinous acid complexes are interesting catalysts exhibiting unique reactivities. In this account, we intend to provide a clear overview of palladium– and platinum–phosphinito–phosphinous acid complexes, their preparation from secondary phosphine oxides, and their applications in catalysis. They have been mainly used to develop [2+1] cycloadditions to afford methylenecyclopropane derivatives using norbornenes and various alkynes as partners. As a function of the catalyst, the reaction conditions, or the nature of the reagents, different synthetic transformations have been observed: [2+1] cycloadditions, giving rise to either alkylidenecyclopropanes or vinylidenecyclopropanes; tandem [2+1]/[3+2] cycloadditions, and so forth. The mechanisms of these reactions have been studied to rationalize the different reactivities observed. 相似文献
8.
Laura Febvay Erwann Hamon Raphaël Recht Nicolas Andres Mathilde Vincent Dalal Aoudé-Werner Hervé This 《Magnetic resonance in chemistry : MRC》2019,57(9):589-602
Roasting of Coffea arabica L. seeds gives rise to chemical reactions that produce more than 800 compounds, some being responsible for the desired organoleptic properties for which the beverage called “coffee” is known. In the industry, the “roasting profile,” that is, the times and temperatures applied, is key to influence the composition of roasted coffee beans and the flavour of the beverage made from them. The impact of roasting on the chemical composition of coffee has been the subject of numerous studies, including by nuclear magnetic resonance (NMR) spectroscopy. However, the roasting equipment and profiles applied in these studies are often far from real industrial conditions. In this work, the effects of two critical technological parameters of the roasting process, namely, the “development time” (the period of time after the “first crack,” a characteristic noise due to seed disruption) and the final roasting temperature on coffee extracts, were investigated. Seeds were roasted at pilot scale according to 13 industrial roasting profiles and extracted in D2O. The extracts were analysed by 1H NMR experiments. The NMR spectra were compared using (a) quantitative analysis of main signals by successive orders of magnitude and (b) chemometric tools (principal component analysis, partial least squares and sparse-orthogonal partial least squares analysis). This allowed to identify compounds, which may serve as markers of roasting and showed that changes in chemical composition can be detected even for slight change in final temperature (~1°C) or in total roasting time (~25 s). 相似文献
9.
Numerical Algorithms - We explain in this article how the famous Belgian astronomer and physicist Georges Lemaître, a specialist in the theory of relativity, rediscovered, during the Second... 相似文献