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51.
Yasmine S. Zubi Bingqing Liu Yifan Gu Dipankar Sahoo Jared C. Lewis 《Chemical science》2022,13(5):1459
Visible light photocatalysis enables a broad range of organic transformations that proceed via single electron or energy transfer. Metal polypyridyl complexes are among the most commonly employed visible light photocatalysts. The photophysical properties of these complexes have been extensively studied and can be tuned by modifying the substituents on the pyridine ligands. On the other hand, ligand modifications that enable substrate binding to control reaction selectivity remain rare. Given the exquisite control that enzymes exert over electron and energy transfer processes in nature, we envisioned that artificial metalloenzymes (ArMs) created by incorporating Ru(ii) polypyridyl complexes into a suitable protein scaffold could provide a means to control photocatalyst properties. This study describes approaches to create covalent and non-covalent ArMs from a variety of Ru(ii) polypyridyl cofactors and a prolyl oligopeptidase scaffold. A panel of ArMs with enhanced photophysical properties were engineered, and the nature of the scaffold/cofactor interactions in these systems was investigated. These ArMs provided higher yields and rates than Ru(Bpy)32+ for the reductive cyclization of dienones and the [2 + 2] photocycloaddition between C-cinnamoyl imidazole and 4-methoxystyrene, suggesting that protein scaffolds could provide a means to improve the efficiency of visible light photocatalysts.Artificial metalloenzyme visible light photocatalysts possess enhanced optical properties and are competent towards single electron and energy transfer organic transformations. 相似文献
52.
Nonlinear Dynamics - An experimental study of the single-well and twin-well, also referred to as intra-well and inter-well, respectively, nonlinear dynamics of a bistable composite laminate is... 相似文献
53.
Martin L. Kaplan Robert C. Haddon Krishnan Raghavachari Shalini Menezes Frederic C. Schilling Jacques J. Hauser 《Molecular Crystals and Liquid Crystals》2013,570(1):51-66
Four compounds, N,N,N',N'-tetramethyl-p-phenylene diamine, N,N,N',N'-tetramethyl-benzidine, 4,4'-bis(dimethylamino)azobenzene and bis(4-dimethylaminophenylimino)sulfur (BAPIS) were examined electrochemically and spectroscopically. Each was shown to be a fairly good donor forming in its first oxidation state a radical-cation. The latter two materials surprisingly exhibited only single one-electron oxidations. Conformational flexibility about the -NSN- unit was studied by NMR spectroscopy and ab initio molecular orbital theory. The experimental ΔG* for a cis-trans to trans-cis interconversion in BAPIS was found to be 11.9 kcal/mole. The four donors all form 1:1 adducts with TCNQ. The compaction resistances of the complexes have been measured as a function of temperature. Of the four, (BAPIS)(TCNQ) appears to be a one-dimensional material. The other three complexes behave as typical mixed stack organic semiconductors. 相似文献
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Pei Li Qichao Zhao Jared L. Anderson Sasidhar Varanasi Maria R. Coleman 《Journal of polymer science. Part A, Polymer chemistry》2010,48(18):4036-4046
Block copolyimides based on aromatic dianhydrides and diamines copolymerized with diamino room temperature ionic liquid (RTIL) monomers were synthesized over a range of compositions. Specifically, two diamino RTILs, 1,3‐di(3‐aminopropyl) imidazolium bis[(trifluoromethyl)sulfonyl] imide ([DAPIM] [NTf2]) and 1,12‐di[3‐(3‐aminopropyl) imidazolium] dodecane bis[(trifluoromethyl) sulfonyl] imide ([C12 (DAPIM)2] [NTf2]2) were synthesized using a Boc protection method. The two RTILs were reacted with 2,2‐bis(3,4‐carboxylphenyl) hexafluoropropane dianhydride (6FDA) to produce 6FDA‐RTILs oligomers that formed the RTIL component for the block copolyimides. The oligomers were reacted with 6FDA and m‐phenylenediamine (MDA) at oligomer concentration from 6.5 to 25.8 mol % to form block copolyimides. Increasing the concentration of the 6FDA‐RTIL oligomer in the block copolyimides resulted in a decrease in the thermal degradation temperature, glass transition temperature and an increase in the density. The gas permeability of the RTIL based block copolyimide decreased but the ideal permeability selectivity for CO2/CH4 gas pair increased relative to the pure 6FDA‐MDA. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4036–4046, 2010 相似文献
58.
In this study, neutron-emission spectra produced by (n, xn) reactions for some structural fusion materials as 27Al, 51V, 52Cr, 55Mn, and 56Fe have been investigated by a neutron beam up to 16 MeV. Multiple preequilibrium mean-free-path constant from internal transition
and the preequilibrium and equilibrium level-density parameters have been investigated for some (n, xn) neutron-emission spectra calculated in this study. Preequilibrium neutron-emission spectra were calculated by using new-evaluated
hybrid model and geometry-dependent hybrid model, full-exciton model, and cascade-exciton model. The reaction equilibrium
component was calculated by Weisskopf-Ewing model. The obtained results have been discussed and compared with the available
experimental data and found agreement with each other.
The text was submitted by the authors in English. 相似文献
59.
Detoxification of Chemical Warfare Agents Using a Zr6‐Based Metal–Organic Framework/Polymer Mixture 下载免费PDF全文
Dr. Su‐Young Moon Emmanuel Proussaloglou Gregory W. Peterson Dr. Jared B. DeCoste Morgan G. Hall Dr. Ashlee J. Howarth Prof. Joseph T. Hupp Prof. Omar K. Farha 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(42):14864-14868
Owing to their high surface area, periodic distribution of metal sites, and water stability, zirconium‐based metal–organic frameworks (Zr6‐MOFs) have shown promising activity for the hydrolysis of nerve agents GD and VX, as well as the simulant, dimethyl 4‐nitrophenylphosphate (DMNP), in buffered solutions. A hurdle to using MOFs for this application is the current need for a buffer solution. Here the destruction of the simulant DMNP, as well as the chemical warfare agents (GD and VX) through hydrolysis using a MOF catalyst mixed with a non‐volatile, water‐insoluble, heterogeneous buffer is reported. The hydrolysis of the simulant and nerve agents in the presence of the heterogeneous buffer was fast and effective. 相似文献
60.
Kaplan L 《Physical review letters》2002,89(18):184103
Recent images of electron flow through a two-dimensional electron gas device show branching behavior that is reproduced in numerical simulations of motion in a correlated random potential [M. A. Topinka, Nature 410, 183 (2001)]]. We show how such branching arises from caustics in the classical flow and find a simple scaling behavior of the branching under variation of the random potential strength. Analytic results describing statistical properties of the branching are confirmed by classical and quantum numerical tests. 相似文献