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91.
Mohamed E. El‐Khouly Dr. Ki‐Jong Han Dr. Kwang‐Yol Kay Prof. Dr. Shunichi Fukuzumi Prof. Dr. 《Chemphyschem》2010,11(8):1726-1734
Spectroscopic, redox, computational, and electron transfer reactions of the covalently linked zinc porphyrin–triphenylamine–fulleropyrrolidine system are investigated in solvents of varying polarity. An appreciable interaction between triphenylamine and the porphyrin π system is revealed by steady‐state absorption and emission, redox, and computational studies. Free‐energy calculations suggest that the light‐induced processes via the singlet‐excited porphyrin are exothermic in benzonitrile, dichlorobenzene, toluene, and benzene. The occurrence of fast and efficient charge‐separation processes (≈1012 s?1) via the singlet‐excited porphyrin is confirmed by femtosecond transient absorption measurements in solvents with dielectric constants ranging from 25.2 (benzonitrile) to 2.2 (benzene). The rates of the charge separation processes are much less solvent‐dependent, which suggests that the charge‐separation processes occur at the top region of the Marcus parabola. The lifetimes of the singlet radical‐ion pair (70–3000 ps at room temperature) decrease substantially in more polar solvents, which suggests that the charge‐recombination process is occurring in the Marcus inverted region. Interestingly, by utilizing the nanosecond transient absorption spectral technique we can obtain clear evidence about the existence of triplet radical‐ion pairs with relatively long lifetimes of 0.71 μs (in benzonitrile) and 2.2 μs (in o‐dichlorobenzene), but not in toluene and benzene due to energetic considerations. From the point of view of mechanistic information, the synthesized zinc porphyrin–triphenylamine–fulleropyrrolidine system has the advantage that both the lifetimes of the singlet and triplet radical‐ion pair can be determined. 相似文献
92.
Martin Hoefling Francesco Iori Dr. Stefano Corni Dr. Kay‐Eberhard Gottschalk Dr. 《Chemphyschem》2010,11(8):1763-1767
The interactions of amino acids with inorganic surfaces are of interest for biologists and biotechnologists alike. However, the structural determinants of peptide–surface interactions have remained elusive, but are important for a structural understanding of the interactions of biomolecules with gold surfaces. Molecular dynamics simulations are a tool to analyze structures of amino acids on surfaces. However, such an approach is challenging due to lacking parameterization for many surfaces and the polarizability of metal surfaces. Herein, we report DFT calculations of amino acid fragments in vacuo and molecular dynamics simulations of the interaction of all amino acids with a gold(111) surface in explicit solvent, using the recently introduced polarizable gold force field GolP. We describe preferred orientations of the amino acids on the metal surface. We find that all amino acids preferably interact with the gold surface at least partially with their backbone, underlining an unfolding propensity of gold surfaces. 相似文献
93.
Thuro Arnold Kay Großmann Nils Baumann 《Analytical and bioanalytical chemistry》2010,396(5):1641-1653
Biofilms may immobilize toxic heavy metals in the environment and thereby influence their migration behaviour. The mechanisms
of these processes are currently not understood, because the complexity of such biofilms creates many discrete geochemical
microenvironments which may differ from the surrounding bulk solution in their bacterial diversity, their prevailing geochemical
properties, e.g. pH and dissolved oxygen concentration, the presence of organic molecules, e.g. metabolites, and many more,
all of which may affect metal speciation. To obtain such information, which is necessary for performance assessment studies
or the development of new cost-effective strategies for cleaning waste waters, it is very important to develop new non-invasive
methods applicable to study the interactions of metals within biofilm systems. Laser fluorescence techniques have some superior
features, above all very high sensitivity for fluorescent heavy metals. An approach combining confocal laser scanning microscopy
and laser-induced fluorescence spectroscopy for study of the interactions of biofilms with uranium is presented. It was found
that coupling these techniques furnishes a promising tool for in-situ non-invasive study of fluorescent heavy metals within
biofilm systems. Information on uranium speciation and uranium redox states can be obtained. 相似文献
94.
We identify conditions under which correlations resulting from quantum measurements performed on macroscopic systems (systems composed of a number of particles of the order of the Avogadro number) can be described by local realism. We argue that the emergence of local realism at the macroscopic level is caused by an interplay between the monogamous nature of quantum correlations and the fact that macroscopic measurements do not reveal properties of individual particles. 相似文献
95.
Jewart CM Chen T Lindner E Fiebrandt J Rothhardt M Schuster K Kobelke J Bartelt H Chen KP 《Optics letters》2011,36(23):4491-4493
This Letter presents simulation and experimental results that explore bending insensitivity of fiber Bragg gratings in suspended-core optical fibers. The implementation of thin silica bridge in the fibers enhances index contrast of the fiber core and reduces bending-induced strain transfer to the fiber core. This fiber design lead to a reduction of over 7 times in strain-induced fiber Bragg grating resonant peak shifts in the suspended-core fiber compared with that in standard telecommunication fiber, and an 0.14 dB bending loss at a bending radius of 6.35 mm. 相似文献
96.
97.
98.
Kay Gore 《School science and mathematics》1986,86(3):263-265
Computer Science II: File Structure Charged Particles II South Dakota: An Economic and Math Simulation 相似文献
99.
100.
Inhomogeneous broadening of resonance lines causes a reduction of absorption in nuclear resonance experiments. This is particularly devastating to the observation of the Mössbauer effect in isomers like 107Ag with a half-life of 44s.It has been suggested in the literature that homogeneous broadening can provide overlap of resonance lines and thus theMössbauer effect can be recovered. The analysis presented in this paper shows that this is not the case for Mössbauer experiments, unless the radiative width ΓΓ also increases. Although overlap occurs when the lines are homogeneously broadened to a total width Γ_H which exceeds the natural width Γ, and the inhomogeneous width Δ, the Mössbauer absorption remains low because it is proportional to the factor of Γγ/Γ H. 相似文献