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71.
Gournis D Georgakilas V Karakassides MA Bakas T Kordatos K Prato M Fanti M Zerbetto F 《Journal of the American Chemical Society》2004,126(27):8561-8568
Three fulleropyrrolidine derivatives, characterized by the presence of positive charges, were introduced in the interlayer space of montmorillonite. The composites were characterized by powder X-ray diffraction and differential thermal and thermogravimetric (DTA-TGA) analysis, in conjunction with FTIR, UV-Vis, Raman, and (57)Fe-M?ssbauer spectroscopies. Organophilic derivatives were intercalated into organically modified clays, while water-soluble fulleropyrrolidines were introduced into the clay galleries through ion exchange. The experiments, complemented by computer simulations, show that not all the clay-clay platelets are intercalated by the fullerene derivatives and that a sizable amount of charge transfer takes place between the host and the guests. 相似文献
72.
Bacchi A Costa M Gabriele B Pelizzi G Salerno G 《The Journal of organic chemistry》2002,67(13):4450-4457
A variety of prop-2-ynylamides have been carbonylated under oxidative conditions to give oxazolines, oxazolines with chelating groups, and bisoxazolines bearing an (alkoxycarbonyl)methylene chain at the 5 position in good yields. The cyclization-alkoxycarbonylation process was carried out in alcoholic media at 50-70 degrees C and under 24 bar pressure of 3:1 carbon monoxide/air in the presence of catalytic amounts of 10% Pd/C or PdI2 in conjunction with KI. Cyclization occurred by anti attack of an oxygen function on the palladium-coordinated triple bond, followed by stereospecific alkoxycarbonylation, strictly resulting in E-stereochemistry. The structures of representative oxazolines and bisoxazolines have been determined by X-ray diffraction analysis. 相似文献
73.
Biscarini F Cavallini M Leigh DA León S Teat SJ Wong JK Zerbetto F 《Journal of the American Chemical Society》2002,124(2):225-233
The first statistical analyses of the X-ray crystal structures of mechanically interlocked molecular architectures, the first molecular mechanics-based solid-state calculations on such structures and atomic force microscopy (AFM) experiments are used in combination to predict and test which types of benzylic amide macrocycle-containing rotaxanes possess mobile components in the crystalline phase and thus could form the basis of solid-state devices that function through mechanical motion at the molecular level. The statistical studies and calculations show that crystals formed by rotaxanes possess similarities and unanticipated differences with respect to the crystal packing of noninterlocked molecules. Trends in the rotaxane series correlate quantities related to crystal packing, molecular size, stoichiometry, and H-bonding. In accordance with the findings of Gavezzotti et al. for conventional molecular architectures, a principal component analysis (PCA) showed that three vectors related to the size, packing parameters, and stoichiometry are sufficient to describe the crystal properties of benzylic amide macrocycle-containing rotaxanes. When hydrogen bond-related quantities are included in a second PCA, they combine with the size and the stoichiometry vectors but not with packing-related parameters, indicating that the intramolecular "saturation" of the H-bonds (between the interlocked components) takes precedence over crystal assembly (i.e., intermolecular packing) in these systems. However, cluster analyses also suggest a major role for the energy of interaction between the macrocycle and its crystal environment. The identification of such a "privileged" interaction is of fundamental importance to the development of rotaxanes with in-crystal mobility of one or more of their interlocked components, a prerequisite for the exploitation of molecular level mechanical motion in the solid state. The set of trends found, together with the calculated energies, was used to propose guidelines for which benzylic amide macrocycle-containing rotaxanes are best suited to become building blocks for systems with mobile submolecular units in the crystalline phase. An experimental test of the predictive power of such guidelines was carried out using AFM on a rotaxane and its thread, identified by the study as a promising candidate for solid-state mobility. Intuitively, the rotaxane should be less mobile in the solid state since it has multiple sets of both hydrogen bond donors and acceptors that can form strong inter- and intramolecular H-bonds. Conversely, the thread has no hydrogen bond donors and cannot form such bonds. The AFM experiments, however, confirm the statistical analysis prediction that the rotaxane is considerably more mobile in the solid than the thread. 相似文献
74.
Till MS Essigke T Becker T Ullmann GM 《The journal of physical chemistry. B》2008,112(42):13401-13410
The large interest in long-range proton transfer in biomolecules is triggered by its importance for many biochemical processes such as biological energy transduction and drug detoxification. Since long-range proton transfer occurs on a microsecond time scale, simulating this process on a molecular level is still a challenging task and not possible with standard simulation methods. In general, the dynamics of a reactive system can be described by a master equation. A natural way to describe long-range charge transfer in biomolecules is to decompose the process into elementary steps which are transitions between microstates. Each microstate has a defined protonation pattern. Although such a master equation can in principle be solved analytically, it is often too demanding to solve this equation because of the large number of microstates. In this paper, we describe a new method which solves the master equation by a sequential dynamical Monte Carlo algorithm. Starting from one microstate, the evolution of the system is simulated as a stochastic process. The energetic parameters required for these simulations are determined by continuum electrostatic calculations. We apply this method to simulate the proton transfer through gramicidin A, a transmembrane proton channel, in dependence on the applied membrane potential and the pH value of the solution. As elementary steps in our reaction, we consider proton uptake and release, proton transfer along a hydrogen bond, and rotations of water molecules that constitute a proton wire through the channel. A simulation of 8 mus length took about 5 min on an Intel Pentium 4 CPU with 3.2 GHz. We obtained good agreement with experimental data for the proton flux through gramicidin A over a wide range of pH values and membrane potentials. We find that proton desolvation as well as water rotations are equally important for the proton transfer through gramicidin A at physiological membrane potentials. Our method allows to simulate long-range charge transfer in biological systems at time scales, which are not accessible by other methods. 相似文献
75.
Stefano Rossi Mirco Bizzotto Flavio Deflorian Michele Fedel 《Surface and interface analysis : SIA》2019,51(12):1194-1206
Aluminium foam is obtained by the production of air into metallic melt. This material shows a very low density together with good mechanical properties, high impact energy absorption, and fire resistance. Different production ways to obtain metallic foam are possible. Considering the cost, the Alporas process is particularly interesting. By means of this production method, a block of metallic foam with close cells is obtained. By slicing, foam panels are obtained. The mechanical cut promotes the formation of an open cells texture on the surface. In this last case, the complex morphology of aluminium foam could be a critical point considering the corrosion behavior in aggressive environments, where localized corrosion phenomena, as pitting or crevice corrosion, are likely to occur. The anodizing treatment is one of the most used methods to improve the corrosion resistance of aluminium and aluminium alloys. The aim of this paper is to perform an anodization treatment to enhance the corrosion resistance of aluminium foam. Constant voltage anodization (12 V for 60 min) and pulsed current anodization (0.04 A/cm2 for 60 seconds and 0.01 A/cm2 for 15 seconds, repeated for 15 cycles) have been carried out in 15 wt% H2SO4 at 20°C. The anodized samples are observed in cross section by optical and electronic microscopes to investigate the structure of the anodic oxide layer and the presence of defects and to measure the thickness of the layer. The corrosion protection performance and the compactness of layers are evaluated using acetic salt spray test and electrochemical impedance spectroscopy. 相似文献
76.
Trebbi B Dehez F Fowler PW Zerbetto F 《The journal of physical chemistry. B》2005,109(38):18184-18188
Aromatic clusters, found with increased frequency in a set of thermophilic proteins, confer an entropic advantage over mesophilic analogues through introduction of large-amplitude oscillations; this is a source of improved free energy at high temperatures. 相似文献
77.
78.
S. C. Zerbetto L. R. Zink K. M. Evenson E. C. C. Vasconcellos 《International Journal of Infrared and Millimeter Waves》1996,17(6):1041-1047
We report 25 new far-infrared laser lines and 26 heterodyne frequency measurements in hydrazine. The frequencies range from 1.0 to 5.5 THz with most of the frequencies between 2.5 and 4.0 THz. The lines were generated in a high frequency, far-infrared Fabry-Perot laser cavity pumped by a CO2 laser. The cavity has a high Q for wavelengths below 150 µm and uses variable coupling to optimize the power for each line.This work has been financed by the Brazilian Government - Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), and by the United States Government - NASA grant W-18, 623.Contribution of NIST, not subject to U.S. copyright. 相似文献
79.
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