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611.
The vertical apparent mass of the human body exhibits nonlinearity, with the principal resonance frequency reducing as the vibration magnitude increases. Measures of the transmission of vibration to the spine and the pelvis have suggested complex modes are responsible for the dominant resonance during vertical excitation, but the modes present with dual-axis excitation have not been investigated. This study was designed to examine how the apparent mass and transmissibility of the human body depend on the magnitude of vertical excitation and the addition of fore-and-aft excitation, and the relation between the apparent mass and the transmissibility of the body. The movement of the body (over the first, fifth and twelfth thoracic vertebrae, the third lumbar vertebra, and the pelvis) in the fore-and-aft and vertical directions (and in pitch at the pelvis) was measured in 12 male subjects sitting with their hands on their laps during random vertical vibration excitation (over the range 0.25–20 Hz) at three vibration magnitudes (0.25, 0.5 and 1.0 m s?2 rms). At the highest magnitude of vertical excitation (1.0 m s?2 rms) the effect of adding fore-aft vibration (at 0.25, 0.5, and 1.0 m s?2 rms) was investigated. The forces in the vertical and fore-and-aft directions on the seat surface were also measured so as to calculate apparent masses. Resonances in the apparent mass and transmissibility to the spine and pelvis in the fore-and-aft and vertical directions, and pitch transmissibility to the pelvis, shifted to lower frequencies as the magnitude of vertical excitation increased and as the magnitude of the additional fore-and-aft excitation increased. The nonlinear resonant behaviour of the apparent mass and transmissibility during dual-axis vibration excitation suggests coupling between the principal mode associated with vertical excitation and the cross-axis influence of fore-and-aft excitation. The transmissibility measures are consistent with complex modes contributing to motion of the body at the principal resonance: pitch motions of the upper thoracic and lumbar spine, and vertical and fore-aft motion of the pelvis and spine. The mode varies with the magnitude of vertical and fore-and-aft excitation.  相似文献   
612.
We offer a new biogenetic proposal for the origin of the complex alkaloid alstonlarsine A, through rearrangement of the Strychnos alkaloids alstolucines B and F. Further, we provide evidence of the chemical feasibility of this proposal in the facile conversion of synthetic alstolucines into alstonlarsine A through a short, efficient sequence of N-methylation, β-elimination, and a cascade 1,7-hydride shift/Mannich cyclization. We believe that this is the first biogenetic proposal involving the “tert-amino effect”, a hydride-shift-based internal redox trigger of a Mannich cyclization. A further interesting feature of the cascade is that its stereochemical outcome most likely originates in conformational preferences during the hydride shift.  相似文献   
613.
Complexation between pyridines and carboxylic acids is driven by hydrogen bonding. This simple, single hydrogen bond is shown to be capable of serving concomitantly as both the agent of liquid crystallinity and as the coupling bond generating an extended linear chain structure. Three such complexes made from an aromatic diacid and three structurally different bis pyridyls were prepared. In each case the association complex self-assembles into an organized liquid crystalline phase. Discussion of this complexation as a step-growth polymerization process is presented along with an examination of the suitability of various methods for characterizing these materials.  相似文献   
614.
Polystyrene (PS) is one of the least recycled large-volume commodity plastics due to bulkiness of foam products and associated contaminants. PS recycling is also severely hampered by the lack of financial incentive, limited versatility, and poor selectivity of existing methods. To this end, herein we report a thermochemical recycling strategy of “degradation-upcycling” to synthesize a library of high-value aromatic chemicals from PS wastes with high versatility and selectivity. Two cascade reactions are selected to first degrade PS to benzene under mild temperatures, followed by the derivatization thereof utilizing a variety of acyl/alkyl and sulfinyl chloride additives. To demonstrate the versatility, nine ketones and sulfides of cosmetic and pharmaceutical relevance were prepared, including propiophenone, benzophenone, and diphenyl sulfide. The approach is also amenable to sophisticated upcycling reaction designs and can produce desired products stepwise. The facile and versatile approach will provide a scalable and profitable methodology for upcycling PS waste into value-added chemicals.  相似文献   
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617.
Low-valent metal–organic frameworks (LVMOFs) and related materials have gained interest due to their potential applications in heterogeneous catalysis. However, of the few LVMOFs that have been reported, none have shown catalytic activity. Herein, a low-valent metal-organic material constructed from phosphine linkers and IrI nodes is reported. This material is effectively a crystalline, insoluble analogue of Vaska's complex. As such, the material reversibly binds O2 and catalyzes the reductive formation of enamines from amides.  相似文献   
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619.
A mild, scalable (kg) metal-free electrochemical decarboxylation of alkyl carboxylic acids to olefins is disclosed. Numerous applications are presented wherein this transformation can simplify alkene synthesis and provide alternative synthetic access to valuable olefins from simple carboxylic acid feedstocks. This robust method relies on alternating polarity to maintain the quality of the electrode surface and local pH, providing a deeper understanding of the Hofer-Moest process with unprecedented chemoselectivity.  相似文献   
620.
Calcium waves are modeled by parabolic partial differential equations, whose simulation codes contain Krylov subspace methods as computational kernels. This paper presents GPU-based parallel computations for the conjugate gradient method applied to the finite difference discretization of a Poisson equation as prototype problem for the computational kernel. The CUDA algorithm tests the three memory systems of global memory, texture memory, and shared memory of a CUDA-enabled GPU. Due to the caching mechanism and coalesced read/write operations, the CUDA algorithm using global memory and single precision floating point numbers outperforms algorithms accessing texture memory and the shared memory. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   
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