全文获取类型
收费全文 | 215篇 |
免费 | 7篇 |
专业分类
化学 | 148篇 |
晶体学 | 1篇 |
力学 | 17篇 |
数学 | 15篇 |
物理学 | 41篇 |
出版年
2020年 | 6篇 |
2019年 | 3篇 |
2016年 | 8篇 |
2015年 | 5篇 |
2014年 | 5篇 |
2013年 | 4篇 |
2012年 | 9篇 |
2011年 | 14篇 |
2010年 | 8篇 |
2008年 | 3篇 |
2007年 | 8篇 |
2006年 | 11篇 |
2005年 | 7篇 |
2004年 | 7篇 |
2003年 | 8篇 |
2002年 | 8篇 |
2001年 | 6篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1998年 | 5篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 5篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1980年 | 2篇 |
1978年 | 4篇 |
1976年 | 4篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1972年 | 5篇 |
1971年 | 2篇 |
1969年 | 3篇 |
1968年 | 3篇 |
1966年 | 1篇 |
1941年 | 1篇 |
1939年 | 1篇 |
1936年 | 2篇 |
1935年 | 2篇 |
1934年 | 3篇 |
1933年 | 3篇 |
1932年 | 1篇 |
1929年 | 1篇 |
1928年 | 1篇 |
1904年 | 1篇 |
排序方式: 共有222条查询结果,搜索用时 15 毫秒
1.
2.
Jaffe DE Straub PB Adams MR Brown CN Charpak G Cooper WE Crittenden JA Finley DA Glass HD Gray R Hemmi Y Hsiung YB Hubbard JR Jonckheere AM Jöstlein H Kaplan DM Lederman LM Luk KB Maki A Mangeot P McCarthy RL Miyake K Plaag RE Rutherfoord JP Sakai Y Santiard JC Sauli F Smith SR Yoshida T Young KK 《Physical review D: Particles and fields》1989,40(9):2777-2795
3.
In this B3 LYP model study, homoleptic nickel(0) ethyne complexes have been predicted as the catalyst resting state for the title reaction. Ethyne ligand coupling of Ni(C(2)H(2))(3) yields monoethyne nickelacyclopentadiene in the rate-determining step. Ethyne coordination is followed by insertion of an ethyne ligand into the Ni--C sigma bond. A highly strained monoethyne trans-nickelacycloheptatriene is formed. This trans intermediate is unable to reductively eliminate benzene without prior isomerization to a cis-structure. Instead, it rapidly collapses to a nickelacyclononatetraene. Ethyne coordination induces reductive elimination to the cyclooctatetraene complex Ni(eta(2)-C(2)H(2))(eta(2)-C(8)H(8)), followed by facile ligand exchange. Other ethyne coupling pathways have been computed to be less favored. The cyclooctatetraene ligand binds significantly weaker to nickel(0) than ethyne, both for mononuclear, and for dinuclear species. For this reason, C--C bond formation steps at Ni(2)(micro-cot) fragments have been predicted to feature prohibitively high overall reaction barriers. 相似文献
4.
We have monitored the spectra and kinetics of μ-oxo iron (III) tetraphenyl porphyrin. The spectral changes between 460 nm
and 770 nm were observed after excitation with 25 ps fwhm, 355 nm pulse. Kinetic studies from — 100 ps to 4 ns suggest that
after the immediate formation of the excited states a transient species is formed which we assign to the π-caion radical-ferrous
porphyrin pair. This pair decays with a time constant of 600 ps ± 100 ps leaving a small amount of disproportionation reaction
photoproducts. The spectra and kinetics of the transients, were not altered by concentration (0.15 OD – 1.0 OD at 571 nm),
solvent or addition of oxygen. 相似文献
5.
Serber Z Straub W Corsini L Nomura AM Shimba N Craik CS Ortiz de Montellano P Dötsch V 《Journal of the American Chemical Society》2004,126(22):7119-7125
Studying protein components of large intracellular complexes by in-cell NMR has so far been impossible because the backbone resonances are unobservable due to their slow tumbling rates. We describe a methodology that overcomes this difficulty through selective labeling of methyl groups, which possess more favorable relaxation behavior. Comparison of different in-cell labeling schemes with three different proteins, calmodulin, NmerA, and FKBP, shows that selective labeling with [(13)C]methyl groups on methionine and alanine provides excellent sensitivity with low background levels at very low costs. 相似文献
6.
Liane M. Moreau Alexandre Herve Mark D. Straub Dominic R. Russo Rebecca J. Abergel Selim Alayoglu John Arnold Augustin Braun Gauthier J. P. Deblonde Yangdongling Liu Trevor D. Lohrey Daniel T. Olive Yusen Qiao Julian A. Rees David K. Shuh Simon J. Teat Corwin H. Booth Stefan G. Minasian 《Chemical science》2020,11(18):4648
We report the structural properties of ultra-small ThO2 and UO2 nanoparticles (NPs), which were synthesized without strong binding surface ligands by employing a covalent organic framework (COF-5) as an inert template. The resultant NPs were used to observe how structural properties are affected by decreasing grain size within bulk actinide oxides, which has implications for understanding the behavior of nuclear fuel materials. Through a comprehensive characterization strategy, we gain insight regarding how structure at the NP surface differs from the interior. Characterization using electron microscopy and small-angle X-ray scattering indicates that growth of the ThO2 and UO2 NPs was confined by the pores of the COF template, resulting in sub-3 nm particles. X-ray absorption fine structure spectroscopy results indicate that the NPs are best described as ThO2 and UO2 materials with unpassivated surfaces. The surface layers of these particles compensate for high surface energy by exhibiting a broader distribution of Th–O and U–O bond distances despite retaining average bond lengths that are characteristic of bulk ThO2 and UO2. The combined synthesis and physical characterization efforts provide a detailed picture of actinide oxide structure at the nanoscale, which remains highly underexplored compared to transition metal counterparts.ThO2 and UO2 nanoparticles synthesized using a COF-5 template exhibit unpassivated surfaces and provide insight into nanoscale properties of actinides. 相似文献
7.
Straub PB Jaffe DE Glass HD Adams MR Brown CN Charpak G Cooper WE Crittenden JA Finley DA Gray R Hemmi Y Hsiung YB Hubbard JR Jonckheere AM Jöstlein H Kaplan DM Lederman LM Luk KB Maki A Mangeot P McCarthy RL Miyake K Plaag RE Rutherfoord JP Sakai Y Santiard JC Sauli F Smith SR Yoshida T Young KK 《Physical review letters》1992,68(4):452-455
8.
Markus Follmann Nils Griebenow Michael G. Hahn Ingo Hartung Franz‐Josef Mais Joachim Mittendorf Martina Schfer Hartmut Schirok Johannes‐Peter Stasch Friederike Stoll Alexander Straub Peter Jeschke Ralf Nauen Michael Edmund Beck Hans‐Wilhelm Engels Hans‐Georg Pirkl Reinhard Albers Rolf W. Albach Jens Krause Andreas Hoffmann Holger Casselmann Jeff Dormish 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2013,125(36):9503-9503
9.
Simon Ludwanowski Dr. Meral Ari Karsten Parison Somar Kalthoum Paula Straub Nils Pompe Prof. Dr. Stefan Weber Priv.-Doz. Dr. Michael Walter Prof. Dr. Andreas Walther 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(58):13203-13212
Arylazopyrazoles are an emerging class of photoswitches with redshifted switching wavelength, high photostationary states, long thermal half-lives and facile synthetic access. Understanding pathways for a simple modulation of the thermal half-lives, while keeping other parameters of interest constant, is an important aspect for out-of-equilibrium systems design and applications. Here, it is demonstrated that the thermal half-life of a water-soluble PEG-tethered arylazo-bis(o-methylated)pyrazole (AAP) can be tuned by more than five orders of magnitude using simple pH adjustment, which is beyond the tunability of azobenzenes. The mechanism of thermal relaxation is investigated by thorough spectroscopic analyses and density functional theory (DFT) calculations. Finally, the concepts of a tunable half-life are transferred from the molecular scale to the material scale. Based on the photochromic characteristics of E- and Z-AAP, transient information storage is showcased in form of light-written patterns inside films cast from different pH, which in turn leads to different times of storage. With respect to prospective precisely tunable materials and time-programmed out-of-equilibrium systems, an externally tunable half-life is likely advantageous over changing the entire system by the replacement of the photoswitch. 相似文献
10.
Near-infrared photonic crystals with higher-order bandgaps generated by two-photon photopolymerization 总被引:2,自引:0,他引:2
Three-dimensional photonic crystals with bandgaps of 1.5-2.3 mum in wavelength and with gap/midgap ratios of as much as 18% were generated efficiently by two-photon photopolymerization in a liquid resin. From 0.5-1.1-mW femtosecond-pulsed 540-nm light, woodpile structures consisting of 40 layers of elliptically shaped rods spaced at 350-500 nm were fabricated by focusing with a 1.3-N.A. objective. The high degree of correlation in these structures allowed the suppression of infrared transmission by as much as 50% as well as the observation of higher-order bandgaps. We also investigated the decrease in the gap wavelength on reduction of layer spacing, in-plane rod spacing, and rod size. 相似文献