全文获取类型
收费全文 | 753篇 |
免费 | 74篇 |
国内免费 | 90篇 |
专业分类
化学 | 542篇 |
晶体学 | 6篇 |
力学 | 38篇 |
综合类 | 16篇 |
数学 | 134篇 |
物理学 | 181篇 |
出版年
2023年 | 7篇 |
2022年 | 11篇 |
2021年 | 12篇 |
2020年 | 27篇 |
2019年 | 21篇 |
2018年 | 19篇 |
2017年 | 21篇 |
2016年 | 25篇 |
2015年 | 31篇 |
2014年 | 45篇 |
2013年 | 53篇 |
2012年 | 76篇 |
2011年 | 75篇 |
2010年 | 35篇 |
2009年 | 60篇 |
2008年 | 56篇 |
2007年 | 42篇 |
2006年 | 43篇 |
2005年 | 58篇 |
2004年 | 41篇 |
2003年 | 28篇 |
2002年 | 36篇 |
2001年 | 14篇 |
2000年 | 20篇 |
1999年 | 7篇 |
1998年 | 5篇 |
1997年 | 9篇 |
1996年 | 7篇 |
1995年 | 1篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 7篇 |
1988年 | 4篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1979年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有917条查询结果,搜索用时 218 毫秒
1.
Wang Fei Cressault Yann Teulet Philippe Li Huan Yang Ke 《Plasma Chemistry and Plasma Processing》2019,39(4):1049-1069
Plasma Chemistry and Plasma Processing - Gas tungsten arc welding (GTAW), a widely used industrial process, is one of the most intense artificial sources of optical radiation. This paper presents a... 相似文献
2.
Sorin‐Claudiu Roşca Dr. Chiara Dinoi Dr. Elsa Caytan Dr. Vincent Dorcet Prof. Dr. Michel Etienne Prof. Dr. Jean‐François Carpentier Dr. Yann Sarazin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(19):6505-6509
Strontium and calcium (alkaline earth: Ae) olefin complexes stabilised by secondary Ae???F?C and β‐agostic Ae???H?Si interactions are presented. Olefin coordination onto the alkaline earths is plain in the solid state, and it is thermodynamically favoured over the coordination of THF. The existence of the Ae???olefin interactions is corroborated by solution NMR data and DFT computations. The coordination mode of the olefin varies with steric effects and, if enforced, olefin dissociation can be compensated by the other non‐covalent interactions, as supported by DFT computations. 相似文献
3.
星载激光雷达是实现海洋垂直剖面探测的有效工具,也是目前迫切需求的海洋光学遥感手段。对星载海洋激光雷达的波长参数进行评估对保证探测有效性具有重要意义。本文从探测深度和信噪比两方面分析了星载海洋激光雷达探测全球海洋的最佳波长。利用MODIS 10个波段的水体光学特性数据,估算全球海水探测深度及相应的最优波长;并根据太阳夫琅禾费暗线特性,对信号信噪比进行优化。结果表明:在探测深度方面,最优探测波长在488 nm波段的海洋占全球海洋面积的70%左右,并且全球95%以上的海域在488 nm波段的探测深度优于0.8倍的真光层深度;在信噪比方面,相对于488 nm波段,486.134 nm夫琅禾费暗线处采用0.1 nm带宽的滤光片可以将背景光强度降低70%,相应地回波信噪比整体提升了约5.0%。就全球海洋探测来说,使用486.134 nm作为探测波长可以提高探测深度,有效抑制太阳背景光,提高信噪比,因此,486.134 nm是星载海洋激光雷达的最佳工作波长。 相似文献
4.
Dr. Franck Ulm Dr. Yann Cornaton Dr. Jean-Pierre Djukic Prof. Michael J. Chetcuti Prof. Vincent Ritleng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(41):8916-8925
The pentamethylcyclopentadienyl N-heterocyclic carbene nickel complex [Ni(η5-C5Me5)Cl(IMes)] (IMes=1,3-dimesitylimidazol-2-ylidene) efficiently catalyses the anti-Markovnikov hydroboration of alkenes with catecholborane in the presence of a catalytic amount of potassium tert-butoxide, and joins the very exclusive club of nickel catalysts for this important transformation. Interestingly, the regioselectivity can be reversed in some cases by using pinacolborane instead of catecholborane. Mechanistic investigations involving control experiments, 1H and 11B NMR spectroscopy, cyclic voltammetry, piezometric measurements and DFT calculations suggest an initial reduction of the NiII precursor to a NiI active species with the concomitant release of H2. The crucial role of the alkoxo-catecholato-borohydride species resulting from the reaction of potassium tert-butoxide with catecholborane in the formation of an intermediate nickel-hydride species that would then be reduced to the NiI active species, is highlighted. 相似文献
5.
Barium‐Mediated Cross‐Dehydrocoupling of Hydrosilanes with Amines: A Theoretical and Experimental Approach 下载免费PDF全文
Clément Bellini Prof. Dr. Jean‐François Carpentier Dr. Sven Tobisch Dr. Yann Sarazin 《Angewandte Chemie (International ed. in English)》2015,54(26):7679-7683
Alkaline‐earth (most prominently barium) complexes of the type [Ae{N(SiMe3)2}2?(THF)x] and [{N^N}Ae{N(SiMe3)2}?(THF)x] are very active and productive precatalysts (TON=396, TOF up to 3600 h?1; Ca相似文献
6.
Energetic 2,2‐Dimethyltriazanium Salts: A New Family of Nitrogen‐Rich Hydrazine Derivatives 下载免费PDF全文
Dr. Valérian Forquet Dr. Carlos Miró Sabaté Dr. Guy Jacob Dr. Yann Guelou Dr. Henri Delalu Dr. Chaza Darwich 《化学:亚洲杂志》2015,10(8):1668-1675
Amination of 1,1‐dimethylhydrazine with NH2Cl or hydroxylamine‐O‐sulfonic acid yields 2,2‐dimethyltriazanium (DMTZ) chloride ( 3 ) and sulphate ( 4 ), respectively. The DMTZ cation was paired with the nitrogen‐rich anions 5‐aminotetrazolate ( 5 ), 5‐nitrotetrazolate ( 6 ), 5,5′‐azobistetrazolate ( 7 ), and azide ( 8 ), yielding a new family of energetic salts. The synthesis was carried out by metathesis reactions of salts 3 or 4 and a suitable silver or barium salt. To minimize the risks involved when using heavy metal salts, we used electrodialysis for the synthesis of azide 8 , which avoids the use of highly sensitive species. The DMTZ derivatives were characterized by IR and multinuclear NMR spectroscopy, elemental analysis, and X‐ray diffraction. Thermal stabilities were measured using DSC analysis and their sensitivities towards classical stimuli were determined using standard tests. Lastly, the relationship between hydrogen bonding in the solid state and sensitivity is discussed. 相似文献
7.
ZnCl_2溶液中微波辅助SnCl_4催化纤维素制备5-HMF 总被引:1,自引:0,他引:1
ZnCl溶液中微波辅助SnCl催化纤维素制备-HMF 《燃料化学学报》2017,45(3):317-322
将纤维素溶解在ZnCl_2溶液中,以SnCl_4为催化剂,微波下使纤维素降解成5-羟甲基糠醛(5-HMF)。实验考察了微波功率、纤维素的质量、ZnCl_2溶液浓度、反应时间及催化剂与纤维素物质的量比等对5-HMF产率的影响。结果表明,以SnCl_4为催化剂,在优化条件:1.0 g纤维素溶解在100 m L 70%ZnCl_2溶液中,微波功率为420 W,降解反应9 min,SnCl_4与纤维素物质的量比2∶1下,5-HMF的产率达到39.4%。 相似文献
8.
Alina Wildenberg Yann Fenard Maxime Carbonnier Alan Kéromnès Benoîte Lefort Zeynep Serinyel Guillaume Dayma Luis Le Moyne Philippe Dagaut Karl Alexander Heufer 《Proceedings of the Combustion Institute》2021,38(1):543-553
The modern catalytic or enzymatic advances allow the production of novel biofuel. Among them, 1,3-dioxolane can be produced from formaldehyde and ethylene glycol, both can be obtained from biomass. In this study, the oxidation of 1,3-dioxolane is studied at stoichiometric conditions. The ignition delay times of 1,3-dioxolane/O2/inert mixtures were measured in a shock tube and in a rapid compression machine at pressures of 20 to 40 bar and temperatures ranging from 630 to 1300 K. The pressure profiles recorded in the rapid compression machine show a first stage of ignition enlightening the influence of the low temperature chemistry of combustion. Furthermore, mole fraction profiles of the stable intermediates produced during the oxidation of 1,3-dioxolane were measured in a jet-stirred reactor at 10 bar. Following these observations, a detailed kinetic model was developed with reaction rate coefficients and thermochemical data calculated by theoretical calculations or estimated by analogies to suitable molecules. In order to get an insight into the most important reaction pathways brute force sensitivity analysis and reaction pathway analysis were performed with the proposed model and discussed. It became clear that in the fuel-in-air case for the alkylhydroperoxide of 1,3-dioxolane the ring opening beta-scission pathway is favored against the further alkane-like second addition to molecular oxygen, which leads to a limited negative temperature coefficient. 相似文献
9.
Ajoy Ramalingam Heiko Minwegen Yann Fenard Karl Alexander Heufer 《Proceedings of the Combustion Institute》2021,38(1):459-467
Cyclic ethers are important intermediates in the oxidation of hydrocarbons and biofuels. Studying the oxidation and pyrolysis of cyclic ethers will help in improving our understanding of this functional group and provide consistency to the base mechanism where they play an important role. In this aspect, propylene oxide has been investigated in this study by obtaining ignition delay time measurements in the rapid compression machine and shock tube. The experiments were performed in a range of pressures varying from 10 to 40 bar at different equivalence ratios (0.5–2.0) and dilution percentages. Additionally, speciation measurements in the shock tube at pyrolysis conditions have been performed at a pressure of 40 bar to explore the isomerization pathways. A detailed kinetic mechanism was developed to describe both the oxidation and pyrolysis chemistry of propylene oxide. The mechanism is not only able to predict the data obtained from this study but also reproduces the data from the literature in a consistent trend. For a better understanding of the oxidation and pyrolysis chemistry of propylene oxide, the kinetic analyses were performed using the developed mechanism to comprehend the important reaction pathways and sensitive reactions. At the investigated regime, the consumption of propylene oxide through its isomerization channels is the critical pathway that controls the reactivity of the fuel. 相似文献
10.
Erwann Le Coz Joanna Hammoud Dr. Thierry Roisnel Marie Cordier Dr. Vincent Dorcet Dr. Samia Kahlal Prof. Dr. Jean-François Carpentier Prof. Dr. Jean-Yves Saillard Dr. Yann Sarazin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(46):11966-11982
Barium complexes ligated by bulky boryloxides [OBR2]− (where R=CH(SiMe3)2, 2,4,6-iPr3-C6H2 or 2,4,6-(CF3)3-C6H2), siloxide [OSi(SiMe3)3]−, and/or phenoxide [O-2,6-Ph2-C6H3]−, have been prepared. A diversity of coordination patterns is observed in the solid state for both homoleptic and heteroleptic complexes, with coordination numbers ranging between 2 and 4. The identity of the bridging ligand in heteroleptic dimers [Ba(μ2-X1)(X2)]2 depends largely on the given pair of ligands X1 and X2. Experimentally, the propensity to fill the bridging position increases according to [OB{CH(SiMe3)2}2)]−<[N(SiMe3)2]−<[OSi(SiMe3)3]−<[O(2,6-Ph2-C6H3)]−<[OB(2,4,6-iPr3-C6H2)2]−. This trend is the overall expression of 3 properties: steric constraints, electronic density and σ- and π-donating capability of the negatively charged atom, and ability to generate Ba ⋅ ⋅ ⋅ F, Ba ⋅ ⋅ ⋅ C(π) or Ba ⋅ ⋅ ⋅ H−C secondary interactions. The comparison of the structural motifs in the complexes [Ae{μ2-N(SiMe3)2}(OB{CH(SiMe3)2}2)]2 (Ae = Mg, Ca, Sr and Ba) suggest that these observations may be extended to all alkaline earths. DFT calculations highlight the largely prevailing ionic character of ligand-Ae bonding in all compounds. The ionic character of the Ae-ligand bond encourages bridging coordination, whereas the number of bridging ligands is controlled by steric factors. DFT computations also indicate that in [Ba(μ2-X1)(X2)]2 heteroleptic dimers, ligand predilection for bridging vs. terminal positions is dictated by the ability to establish secondary interactions between the metals and the ligands. 相似文献