全文获取类型
收费全文 | 449篇 |
免费 | 40篇 |
国内免费 | 1篇 |
专业分类
化学 | 367篇 |
晶体学 | 2篇 |
力学 | 21篇 |
数学 | 53篇 |
物理学 | 47篇 |
出版年
2023年 | 5篇 |
2022年 | 4篇 |
2021年 | 9篇 |
2020年 | 22篇 |
2019年 | 18篇 |
2018年 | 15篇 |
2017年 | 9篇 |
2016年 | 16篇 |
2015年 | 20篇 |
2014年 | 31篇 |
2013年 | 33篇 |
2012年 | 44篇 |
2011年 | 38篇 |
2010年 | 19篇 |
2009年 | 18篇 |
2008年 | 27篇 |
2007年 | 26篇 |
2006年 | 30篇 |
2005年 | 29篇 |
2004年 | 24篇 |
2003年 | 20篇 |
2002年 | 13篇 |
2001年 | 3篇 |
2000年 | 5篇 |
1999年 | 1篇 |
1998年 | 5篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1988年 | 1篇 |
1985年 | 2篇 |
排序方式: 共有490条查询结果,搜索用时 15 毫秒
61.
This paper is devoted to the construction of weak solutions to the singular constant Q-curvature problem. We build on several tools developed in the last years. This is the first construction of singular metrics on closed manifolds of sufficiently large dimension with constant (positive) Q-curvature. 相似文献
62.
Yannick Geiger Thierry Achard Aline Maisse-Franois Stphane Bellemin-Laponnaz 《Chemical science》2020,11(46):12453
The chiral ligand N-methylephedrine (NME) was found to catalyse the addition of dimethylzinc to benzaldehyde in an enantiodivergent way, with a monomeric and a homochiral dimeric complex both catalysing the reaction at a steady state and giving opposite product enantiomers. A change in the sign of the enantiomeric product was thus possible by simply varying the catalyst loading or the ligand ee, giving rise to an enantiodivergent non-linear effect. Simulations using a mathematical model confirmed the possibility of such behaviour and showed that this can lead to situations where a reaction gives racemic products, although the system is composed only of highly enantioselective individual catalysts. Furthermore, depending on the dimer''s degree of participation in the catalytic conversion, enantiodivergence may or may not be observed experimentally, which raises questions about the possibility of enantiodivergence in other monomer/dimer-catalysed systems. Simulations of the reaction kinetics showed that the observed kinetic constant kobs is highly dependent on user-controlled parameters, such as the catalyst concentration and the ligand ee, and may thus vary in a distinct way from one experimental setup to another. This unusual dependency of kobs allowed us to confirm that a previously observed U-shaped catalyst order vs. catalyst loading-plot is linked to the simultaneous catalytic activity of both monomeric and dimeric complexes.An asymmetric reaction consisting of competing monomeric and dimeric catalysts may explain enantiodivergent non-linear effects. 相似文献
63.
Belgacem Bezzina Rayenne Djémil Djamel eddine Khatmi Stéphane Humbel Yannick Carissan 《Journal of inclusion phenomena and macrocyclic chemistry》2018,91(1-2):115-124
A high-efficiency microwave irradiation (MW) assisted protocol was proposed to synthesize series SPE-β-CD with specific degree of substitution (DS) in the sodium hydroxide solution. This protocol provided an eco-friendly way to modify the cyclodextrins with bulky sulfopropyl substituent on the purpose of avoiding organic solvents and high quantities of thermal energy. Temperature and energy distribution became more uniform under the new method accordingly. Therefore, not only the reaction time reduced significantly from over 20 h to a few hours, but also the DS increased up according to 1H NMR spectroscopy, MS and elemental analysis results. Most importantly, the effects of reaction parameters on DS were compared both under MW method and conventional heating method, and were sufficiently studied to guarantee the aforementioned results could be better reproduced and DS of products could become more specific through the synthesis process. Products structures were characterized by FT-IR, DSC, and 13C NMR spectroscopy. 相似文献
64.
This paper examines the preparation of tailor-made azaporphyrins and analogues exhibiting their Q-bands in several particular and predetermined regions of the electromagnetic spectrum. The applications of phthalocyanines, the possibility of preparing novel related porphyrinoids with different colour properties and, consequently, new emerging applications, are discussed. 相似文献
65.
Mercier Y Santoro F Reguero M Improta R 《The journal of physical chemistry. B》2008,112(35):10769-10772
By integrating the results of MS-CASPT2/CASSCF and TD-PBE0 calculations, we propose a mechanism for the decay of the excited dark state in pyrimidine, fully consistent with all the available experimental results. An effective conical intersection (CI-npi) exists between the spectroscopic pi/pi* excited state (Spi) and a dark n/pi* state (Sn), and a fraction of the population decays to the minimum of Sn (Sn-min). The conical intersection between Sn and the ground-state is not involved in the decay mechanism, because of its high energy gap with respect to Sn-min. On the other hand, especially in hydrogen bonding solvents, the energy gap between Sn-min and CI-npi is rather small. After thermalization in Sn-min, the system can thus recross CI-npi and then quickly proceed on the Spi barrierless path toward the conical intersection with the ground state. 相似文献
66.
Listorti A Accorsi G Rio Y Armaroli N Moudam O Gégout A Delavaux-Nicot B Holler M Nierengarten JF 《Inorganic chemistry》2008,47(14):6254-6261
Heteroleptic copper(I) complexes CuPOP-F and CuFc-F have been prepared from a fullerene-substituted phenanthroline ligand and bis[2-(diphenylphosphino)phenyl] ether (POP) and 1,1'-bis(diphenylphosphino)ferrocene (dppFc), respectively. Electrochemical studies indicate that some ground-state electronic interaction between the fullerene subunit and the metal-complexed moiety are present in both CuPOP-F and CuFc-F. Their photophysical properties have been investigated by steady state and time-resolved UV-vis-NIR luminescence spectroscopy and nanosecond laser flash photolysis in a CH2Cl2 solution and compared to those of the corresponding model copper(I) complexes CuPOP and CuFc and of the fullerene model compound F. Selective excitation of the methanofullerene moiety in CuPOP-F results in regular deactivation of the lowest singlet and triplet states, indicating no intercomponent interactions. Conversely, excitation of the copper(I)-complexed unit (405 nm, 40% selectivity) shows that the strongly luminescent triplet metal-to-ligand charge-transfer ((3)MLCT) excited state located at 2.40 eV is quenched by the carbon sphere with a rate constant of 1.6 x 10(8) s(-1). Details on the mechanism of photodynamic processes in CuPOP-F via transient absorption are hampered by the rather unfavorable partition of light excitation between the two chromophores. By determination of the yield of formation of the lowest fullerene triplet level through sensitized singlet oxygen luminescence in the NIR region, it is shown that the final sink of photoinduced processes is always the fullerene triplet. This can be populated via a two-step charge-separation charge-recombination process and a less favored (3)MLCT --> (3)C60 triplet-triplet energy-transfer pathway. In CuFc-F, both of the photoexcited copper(I)-complexed and fullerene moieties are quenched by the presence of the ferrocene unit, most likely via ultrafast energy transfer. 相似文献
67.
Solution Layer Deposition: A Technique for the Growth of Ultra‐Pure Manganese Oxides on Silica at Room Temperature 下载免费PDF全文
Dr. Jérémy Cure Dr. Kilian Piettre Dr. Yannick Coppel Dr. Eric Beche Dr. Jérôme Esvan Vincent Collière Dr. Bruno Chaudret Dr. Pierre Fau 《Angewandte Chemie (International ed. in English)》2016,55(9):3027-3030
With the ever increasing miniaturization in microelectronic devices, new deposition techniques are required to form high‐purity metal oxide layers. Herein, we report a liquid route to specifically produce thin and conformal amorphous manganese oxide layers on silicon substrate, which can be transformed into a manganese silicate layer. The undesired insertion of carbon into the functional layers is avoided through a solution metal–organic chemistry approach named Solution Layer Deposition (SLD). The growth of a pure manganese oxide film by SLD takes place through the decoordination of ligands from a metal–organic complex in mild conditions, and coordination of the resulting metal atoms on a silica surface. The mechanism of this chemical liquid route has been elucidated by solid‐state 29Si MAS NMR, XPS, SIMS, and HRTEM. 相似文献
68.
NIR‐to‐NIR Two‐Photon Scanning Laser Microscopy Imaging of Single Nanoparticles Doped by YbIII Complexes 下载免费PDF全文
Dr. Adrien Bourdolle Dr. Anthony D'Aléo Dr. Cécile Philippot Dr. Patrice L. Baldeck Dr. Yannick Guyot Dr. Fabien Dubois Dr. Alain Ibanez Dr. Chantal Andraud Dr. Sophie Brasselet Dr. Olivier Maury 《Chemphyschem》2016,17(1):128-135
The photophysical and nonlinear optical properties of water‐soluble chromophore‐functionalised tris‐dipicolinate complexes [LnL3]3? (Ln=Yb and Nd) are thoroughly studied, revealing that only the YbIII luminescence can be sensitized by a two‐photon excitation process. The stability of the complex in water is strongly enhanced by embedding in dispersible organosilicate nanoparticles (NPs). Finally, the spectroscopic properties of [NBu4]3[YbL3] are studied in solution and in the solid state. The high brightness of the NPs allows imaging them as single objects using a modified two‐photon microscopy setup in a NIR‐to‐NIR configuration. 相似文献
69.
Julien Racine Denis Hagebaum‐Reignier Yannick Carissan Stéphane Humbel 《Journal of computational chemistry》2016,37(8):771-779
A method is proposed to obtain coefficients and weights of valence bond (VB) determinants from multi configurational wave functions. This reading of the wave functions can apply to ground states as well as excited states. The method is based on projection operators. Both energetic and overlap‐based criteria are used to assess the quality of the resulting VB wave function. The approach gives a simple access to a VB rewriting for low‐lying states, and it is applied to the allyl cation, to the allyl radical and to the ethene (notably to the V‐state). For these states, large overlap between VB and multi reference wave functions are easily obtained. The approach proves to be useful to propose an interpretation of the nature of the V‐state of ethene. © 2015 Wiley Periodicals, Inc. 相似文献
70.