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51.
Kaustuv Das Alexandra V. Smirnov Jin Wen Pavol Miskovsky Jacob W. Petrich 《Photochemistry and photobiology》1999,69(6):633-645
Time-resolved fluorescence and absorption measurements are performed on hypericin complexed with human serum albumin, HSA (1:4, 1:1 and approximately 5:1 hypericin: HSA complexes). Detailed comparisons with hypocrellin A/HSA complexes (1:4 and 1:1) are made. Our results are consistent with the conclusions of previous studies indicating that hypericin binds to HSA by means of a specific hydrogen-bonded interaction between its carbonyl oxygen and the N1-H of the tryptophan residue in the IIA subdomain of HSA. (They also indicate that some hypericin binds nonspecifically to the surface of the protein.) A single-exponential rotational diffusion time of 31 ns is measured for hypericin bound to HSA, indicating that it is very rigidly held. Energy transfer from the tryptophan residue of HSA to hypericin is very efficient and is characterized by a critical distance of 94 A, from which we estimate a time constant for energy transfer of approximately 3 x 10(-15) s. Although it is tightly bound to HSA, hypericin is still capable of executing excited-state intramolecular proton (or hydrogen atom) transfer in the approximately 5:1 complex, albeit to a lesser extent than when it is free in solution. It appears that the proton transfer process is completely impeded in the 1:1 complex. The implications of these results for hypericin (and hypocrellin A) are discussed in terms of the mechanism of intramolecular excited-state proton transfer, the mode of binding to HSA and the light-induced antiviral and antitumor activity. 相似文献
52.
Pavol Brunovský 《Journal of Dynamics and Differential Equations》1990,2(3):293-323
For the scalar reaction diffusion equation with Dirichlet boundary conditions, it is proved that its maximal compact attractor is the graph of a C1 function from a subset with nonempty interior of a subspace of the state space the dimension of which is equal to the maximal Morse index of the equilibria of the equation. 相似文献
53.
Pavol Brunovský Peter Poláčik 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1987,38(2):172-183
Summary The problem of generic hyperbolicity for reaction diffusion equations with Dirichlet boundary conditions on a ball inR
n
is studied. It is proved that while hyperbolicity is not a generic property, radially symmetric solutions are generically hyperbolic.
Zusammenfassung Das Problem der generischen Hyperbolizität für Reaktion-Diffusionsgleichungen mit Dirichletschen Randbedingungen in einer Kugel imR n wird betrachtet. Es wird bewiesen, daß radialsymmetrische Lösungen generisch symmetrische sind, während Hyperbolizität nicht eine generische Eigenschaft ist.相似文献
54.
Dimethyl 2‐{[2‐(methoxycarbonyl)‐1‐(methoxycarbonylmethyl)pyrrol‐4‐yl]methylene}propanedioate
Jan Lokaj Viktor Kettmann Viktor Milata Pavol Hodul Peter Kotta Ognyan Petrov 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(8):973-974
The title compound, C15H17NO8, is a pyrrole–ethene derivative with potential biological activity. Although a large part of the molecule is planar, there is no structural evidence for any conjugation push–pull effect across the ethylenic bond, which is usually observed for substituted ethylenes; π‐electron delocalization appears to be restricted to the 2‐(methoxycarbonyl)pyrrole moiety. 相似文献
55.
56.
57.
Hrdlovic P Donovalova J Stankovicova H Gaplovsky A 《Molecules (Basel, Switzerland)》2010,15(12):8915-8932
Absorption and fluorescence spectra of bichromophoric coumarins were investigated in different solvents and in polymer matrices. These bichromophoric coumarins were composed of a coumarin dimethylamino-substituted at position 7 or unsubstituted coumarin and phthalimide or a 1,8-naphthylimide linked with an iminomethyl bridge to the position 3 or 8 of the coumarin ring. Absorption spectra of 7-dimethylamino derivatives in position 3 of coumarin were quite similar, exhibiting broad bands around 430-440 nm like the parent compound 7-dimethylaminocoumarin-3-carbaldehyde. For coumarin derivatives substituted in position 8, the absorption maximum was shifted to shorter wavelength as for derivatives without position 7 dimethylamino substitution. The most intense fluorescence was observed for 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin in polar solvent, while intense fluorescence was observed for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxobenz[de]isoquinolinyl)iminomethyl]-coumarin in non polar solvent (chloroform), comparable with the fluorescence of 7-amino-4-methylcoumarin. Spectral measurements of bichromophoric coumarins in polymer matrices revealed that the maxima lies in between those for chloroform and methanol yielding more intense fluorescence then in solutions. Completely different solvent effects were observed for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxobenz[de]isoquinolinyl)imino-methyl]coumarin and 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin. With addition of polar methanol the intensity of fluorescence decreases, yielding a Stern-Volmer-like constant of 0.54 dm3 mol?1 for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxo-benz[de]isoquinolinyl)iminomethyl]coumarin and an even higher one of 1.08 dm3·mol?1 for 7-dimethylaminocoumarin-3-carbaldehyde compared to the rather low one of 0.024 dm3 mol?1 for 7-amino-4-methylcoumarin. Contrary to this, addition of methanol under identical conditions brings about an increase in fluorescence intensity of 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin (about 60-fold). The reasons for these different solvent effects are discussed. 相似文献
58.
Dominika Valachová Michaela Marčeková Dr. Oľga Caletková Dr. Andrej Kolarovič Dr. Pavol Jakubec 《European journal of organic chemistry》2023,26(13):e202201341
Protodenitration, a direct reduction of nitroalkanes to corresponding alkanes, already spans two centuries and is enabled by various reagents. This mini-review provides a historical development of the fundamental transformation and highlights the governing position of the Ono-Tanner reaction employing tributyltin hydride. Due to the unchallenged dominance of the toxic tributyltin hydride and environmentally unpopular solvents sharply contrasting with modern ecological trends, the current situation was dubbed “the last fortress of tin's tyranny.” 相似文献
59.
This study examines the alkylation of diphenylamine (DPA) with nonene (NON) in a liquid phase catalyzed by acid-treated clay-based catalysts from commercial suppliers (Fulcat 22B, Nobelin MM, and Jeltar 300). Alkylations were conducted to achieve the highest possible selectivity of diisononyldiphenylamine (DNDPA), low selectivity of monoisononyldiphenylamine, and a maximum triisononyldiphenylamine yield of 4%. This study also examines the reaction conditions to selectively form dialkylated diphenylamine from DPA and NON in a batch reactor. Repeated use of the catalyst during the alkylation of DPA with NON was also investigated. Catalyst deactivation takes place during the alkylation of each batch and intensifies with repeated catalyst use, resulting in low DNDPA selectivity. The regenerated catalyst was sufficiently active only until the regeneration of the first and second batches. After the third batch, the catalyst’s selectivity for DNDPA was very low, and its reuse in the alkylation of DPA with NON was not efficient. Therefore, to achieve the maximum length of catalyst activity, the fresh catalyst was gradually added to the used catalyst from a previous batch, thus maintaining a high activity of eight batches. The reduction in catalyst activity was probably caused by the irreversible adsorption of substances on the surface, a loss of microporous structure, and a loss of surface acidity. DPA or alkylated products are adsorbed on the surface oxygen of the catalyst through nitrogen and form nitro formations. The fresh and regenerated catalysts were characterized by their surface area, surface acidity, pore size distribution, and pore volume. 相似文献
60.