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51.
Transalkylation of Higher Trifluoromethylated Fullerenes with C70: A Pathway to New Addition Patterns of C70(CF3)8
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Nikita M. Belov Marina G. Apenova Alexey V. Rybalchenko Eugenia V. Borkovskaya Dr. Natalia S. Lukonina Dr. Alexey A. Goryunkov Dr. Ilya N. Ioffe Prof. Dr. Sergey I. Troyanov Prof. Dr. Lev N. Sidorov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):1126-1133
We report three new isomers of C70(CF3)8, structurally related to p7mp‐C70(CF3)10, that are inaccessible by direct trifluoromethylation, but can be easily identified among the products of the transalkylation of higher trifluoromethylfullerenes with C70. The reported compounds are characterized by UV/Vis, 1 D and 2 D COSY 19F NMR spectroscopy, and DFT calculations. A rather unusual addition pattern is observed in p6,i‐C70(CF3)8 in which one addend is attached remotely from the others; polarization of the adjacent unsaturated bonds by the addend makes the molecule readily oxidizable. 相似文献
52.
Atomic-level studies of protein activity represent a significant challenge as a result of the complexity of conformational changes occurring on wide-ranging timescales, often greatly exceeding that of even the longest simulations. A prime example is the elucidation of protein allosteric mechanisms, where localized perturbations transmit throughout a large macromolecule to generate a response signal. For example, the conversion of chemical to electrical signals during synaptic neurotransmission in the brain is achieved by specialized membrane proteins called pentameric ligand-gated ion channels. Here, the binding of a neurotransmitter results in a global conformational change to open an ion-conducting pore across the nerve cell membrane. X-ray crystallography has produced static structures of the open and closed states of the proton-gated GLIC pentameric ligand-gated ion channel protein, allowing for atomistic simulations that can uncover changes related to activation. We discuss a range of enhanced sampling approaches that could be used to explore activation mechanisms. In particular, we describe recent application of an atomistic string method, based on Roux's “swarms of trajectories” approach, to elucidate the sequence and interdependence of conformational changes during activation. We illustrate how this can be combined with transition analysis and Brownian dynamics to extract thermodynamic and kinetic information, leading to understanding of what controls ion channel function. © 2019 Wiley Periodicals, Inc. 相似文献
53.
Lev S. Zarkhin Leonid I. Manevitch Nikolai S. Enikolopian 《Macromolecular Symposia》1989,26(1):431-450
Elementary events in polymer fracture at the molecular level are the breakdowns of single polymeric chains. Breakdown of a stretched macromolecule is accompanied by its mechanical degradation. Comparison of experimental data on the molecular products of thermal and mechanical degradation points to significant distinctions between these two processes. Generation of highly excited (“hot”) molecular products of mechanical degradation by the growing crack cannot be explained in terms of the kinetic concept of polymer fracture. Elaborate theoretical analysis of polymeric chain breakdown and generation of “hot” molecular products in subpicosecond time range is made by numerical molecular dynamic simulation with a computer. The mechanisms of primary and secondary chain breakdowns are established. The principal initiators of breakdowns are localized nonlinear modes of the lattice soliton type. Generation of highly excited (“hot”) molecular products occurs at the initial stage of mechanical degradation (during≈1 picosecond after the first breakdown). 相似文献
54.
Physics of Particles and Nuclei Letters - Physicists usually understand that physics cannot (and should not) derive that $$c \approx 3 \times {{10}^{8}}$$ m/s and $$\hbar \approx 1.054 \times... 相似文献
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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
58.
Lev Vaidman 《Foundations of Physics》1999,29(6):865-876
This paper is an answer to the preceding paper by Kastner, in which she continued the criticism of the counterfactual usage of the Aharonov-Bergman-Lebowitz rule in the framework of the time-symmetrized quantum theory, in particular, by analyzing the three-box paradox. It is argued that the criticism is not sound. Paradoxical features of the three-box example are discussed. It is explained that the elements of reality in the framework of time-symmetrized quantum theory are counterfactual statements, and therefore, even conflicting elements of reality can be associated with a single system. It is shown how such counterfactual elements of reality can be useful in the analysis of a physical experiment (the three-box example). The validity of Kastner's application of the consistent histories approach to the time-symmetrized counterfactuals is questioned. 相似文献
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One of the more successful techniques for solving zero-one integer programs has been the implicit enumeration strategy first introduced by E. Balas. However, experience has shown that the efficiency of these enumerative techniques depends critically upon the bumber of variables. In this paper an algorithm is developed and computational experience provided for solving zero-one integer programs with many variables and few constraints. Sub-problems solved via implicit enumeration are generated from the linear programming relaxation and the variables in these sub-problems correspond to the fractional variables obtained in the linear program. Since the number of fractional variables in the linear program is bounded by the number of constraints in the linear program, the sub-problems will in general contain many fewer variables than the original zero-one integer program. 相似文献