全文获取类型
收费全文 | 741篇 |
免费 | 54篇 |
国内免费 | 2篇 |
专业分类
化学 | 562篇 |
晶体学 | 1篇 |
力学 | 23篇 |
数学 | 80篇 |
物理学 | 131篇 |
出版年
2023年 | 9篇 |
2022年 | 8篇 |
2021年 | 11篇 |
2020年 | 20篇 |
2019年 | 13篇 |
2018年 | 24篇 |
2017年 | 6篇 |
2016年 | 38篇 |
2015年 | 22篇 |
2014年 | 28篇 |
2013年 | 36篇 |
2012年 | 64篇 |
2011年 | 86篇 |
2010年 | 39篇 |
2009年 | 47篇 |
2008年 | 64篇 |
2007年 | 71篇 |
2006年 | 56篇 |
2005年 | 54篇 |
2004年 | 26篇 |
2003年 | 27篇 |
2002年 | 23篇 |
2001年 | 4篇 |
2000年 | 5篇 |
1999年 | 5篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1981年 | 1篇 |
排序方式: 共有797条查询结果,搜索用时 218 毫秒
111.
Koch R Finnerty JJ Bruhn T Borget F Wentrup C 《The journal of physical chemistry. A》2008,112(38):8999-9004
The complex reaction of thermally generated iminopropadienones with amines in the gas phase and upon matrix deposition and its varying product composition is investigated using density functional theory. In the high energy gas phase addition a single amine molecule reacts readily with iminopropadienone with the decisive step being a 1,3-hydrogen shift and activation barriers of at least 100 kJ/mol. In accordance with the experiment, the formation of ketenes is favored. In the condensed phase of an amine matrix, the utilization of amine dimers both as reagents and as explicit solvents lowers the activation energy required to a feasible 20-30 kJ/mol and predicts ketenimines as the main products, as observed experimentally. 相似文献
112.
Silly F Shaw AQ Castell MR Briggs GA 《Chemical communications (Cambridge, England)》2008,(16):1907-1909
The mixing of perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) and 1,3,5-triazine-2,4,6-triamine (melamine) at room temperature in a ratio of 3 : 4 on Au(111) leads to the formation of a new chiral "pinwheel" structure. 相似文献
113.
Samuel F. Cousin Dr. Pavel Kadeřávek Baptiste Haddou Dr. Cyril Charlier Thorsten Marquardsen Jean‐Max Tyburn Dr. Pierre‐Alain Bovier Dr. Frank Engelke Dr. Werner Maas Prof. Dr. Geoffrey Bodenhausen Dr. Philippe Pelupessy Prof. Dr. Fabien Ferrage 《Angewandte Chemie (International ed. in English)》2016,55(34):9886-9889
Nuclear magnetic resonance (NMR) studies have benefited tremendously from the steady increase in the strength of magnetic fields. Spectacular improvements in both sensitivity and resolution have enabled the investigation of molecular systems of rising complexity. At very high fields, this progress may be jeopardized by line broadening, which is due to chemical exchange or relaxation by chemical shift anisotropy. In this work, we introduce a two‐field NMR spectrometer designed for both excitation and observation of nuclear spins in two distinct magnetic fields in a single experiment. NMR spectra of several small molecules as well as a protein were obtained, with two dimensions acquired at vastly different magnetic fields. Resonances of exchanging groups that are broadened beyond recognition at high field can be sharpened to narrow peaks in the low‐field dimension. Two‐field NMR spectroscopy enables the measurement of chemical shifts at optimal fields and the study of molecular systems that suffer from internal dynamics, and opens new avenues for NMR spectroscopy at very high magnetic fields. 相似文献
114.
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
115.
Ryan M. Bain Christopher J. Pulliam Fabien Thery Prof. R. Graham Cooks 《Angewandte Chemie (International ed. in English)》2016,55(35):10478-10482
Leidenfrost levitated droplets can be used to accelerate chemical reactions in processes that appear similar to reaction acceleration in charged microdroplets produced by electrospray ionization. Reaction acceleration in Leidenfrost droplets is demonstrated for a base‐catalyzed Claisen–Schmidt condensation, hydrazone formation from precharged and neutral ketones, and for the Katritzky pyrylium into pyridinium conversion under various reaction conditions. Comparisons with bulk reactions gave intermediate acceleration factors (2–50). By keeping the volume of the Leidenfrost droplets constant, it was shown that interfacial effects contribute to acceleration; this was confirmed by decreased reaction rates in the presence of a surfactant. The ability to multiplex Leidenfrost microreactors, to extract product into an immiscible solvent during reaction, and to use Leidenfrost droplets as reaction vessels to synthesize milligram quantities of product is also demonstrated. 相似文献
116.
Cover Picture: On The Potential of Dynamic Nuclear Polarization Enhanced Diamonds in Solid‐State and Dissolution 13C NMR Spectroscopy (ChemPhysChem 17/2016) 下载免费PDF全文
117.
Goulay F Osborn DL Taatjes CA Zou P Meloni G Leone SR 《Physical chemistry chemical physics : PCCP》2007,9(31):4291-4300
The reactions of the ethynyl radical (C(2)H) with propyne and allene are studied at room temperature using an apparatus that combines the tunability of the vacuum ultraviolet radiation of the Advanced Light Source at Lawrence Berkeley National Laboratory with time-resolved mass spectrometry. The C(2)H radical is prepared by 193-nm photolysis of CF(3)CCH and the mass spectrum of the reacting mixture is monitored in time using synchrotron-photoionization with a dual-sector mass spectrometer. Analysis using photoionization efficiency curves allows the isomer-specific detection of individual polyynes of chemical formula C(5)H(4) produced by both reactions. The product branching ratios are estimated for each isomer. The reaction of propyne with ethynyl gives 50-70% diacetylene (H-C[triple bond]C-C[triple bond]C-H) and 50-30% C(5)H(4), with a C(5)H(4)-isomer distribution of 15-20% ethynylallene (CH(2)=C=CH-C[triple bond]CH) and 85-80% methyldiacetylene (CH(3)-C[triple bond]C-C[triple bond]CH). The reaction of allene with ethynyl gives 35-45% ethynylallene, 20-25% methyldiacetylene and 45-30% 1,4-pentadiyne (HC[triple bond]C-CH(2)-C[triple bond]CH). Diacetylene is most likely not produced by this reaction; an upper limit of 30% on the branching fraction to diacetylene can be derived from the present experiment. The mechanisms of polyynes formation by these reactions as well as the implications for Titan's atmospheric chemistry are discussed. 相似文献
118.
Duvernay F Chatron-Michaud P Borget F Birney DM Chiavassa T 《Physical chemistry chemical physics : PCCP》2007,9(9):1099-1106
Vacuum ultraviolet (VUV) irradiation of acetamide has been monitored by Fourier transform infrared spectroscopy in argon matrix at 10 K. Several primary photoproducts, including HNCO ratio CH(4) and CO ratio CH(3)NH(2) molecular complexes, and acetimidic acid, which is reported for the first time, were characterized. The acetimidic acid identification was based on comparison between the experimental and theoretical (B3LYP) infrared spectra. Acetimidic acid is found in argon matrix in the (s-Z)-(E) and (s-Z)-(Z) configurations. It is also an intermediate in the VUV decomposition process, its dehydration leads to the formation of CH(3)CN ratio H(2)O molecular complex. The assignment of the complex was achieved by co-depositing the pairs of respective species and by ab initio calculation. 相似文献
119.
Diethylzinc-mediated radical addition to CN bonds was investigated in the presence of phenylorganotellurium compounds as radical precursors. As group transfer agents, secondary alkyl phenyl tellurides were shown to be about twice as reactive as the corresponding alkyl iodides towards ethyl radical. Their use was proven to be advantageous regarding both chemoselectivity and yield. The replacement of diethylzinc by dimethylzinc, offers no advantage in these reactions. 相似文献
120.
Durola F Russo L Sauvage JP Rissanen K Wenger OS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(31):8749-8753
3,3'-biisoquinoline ligands (biiq) L, bearing aromatic substituents on their 8 and 8' positions, have been used to generate interwoven systems consisting of three crescent-shaped ligands disposed around an octahedral metal centre. Mono-ligand complexes of the type [ReL(CO)3py]+ (py: pyridine) have also been prepared, leading to sterically non-hindering complexes in spite of the endotopic nature of the chelate used. The three-component entanglements have been prepared by using either FeII or RuII as gathering metal centre. The synthetic procedure is simple and efficient, affording fully characterised complexes as their PF6 or SbCl6 salts. X-ray crystallography clearly shows that the crescent-shaped ligands do not repel each other in the tris-chelate complexes. In an analogous way, the ReI complexes show open structures with no steric repulsion between the L ligand and the ancillary CO or py groups. The FeL3 or RuL3 compounds are very unusual in the sense that, contrary to all the other tris-bidentate chelate complexes made till now, the three organic components are tangled up, in a situation which will be very favourable to the formation of new non trivial topologies of the catenane type. 相似文献