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991.
High-resolution, >1 GHz NMR in unstable magnetic fields 总被引:3,自引:0,他引:3
Resistive or hybrid magnets can achieve substantially higher fields than those available in superconducting magnets, but their spatial homogeneity and temporal stability are unacceptable for high-resolution NMR. We show that modern stabilization and shimming technology, combined with detection of intermolecular zero-quantum coherences (iZQCs), can remove almost all of the effects of inhomogeneity and drifts, while retaining chemical shift differences and J couplings. In a 25-T electromagnet (1 kHz/s drift, 3 kHz linewidth over 1 cm(3)), iZQC detection removes >99% of the remaining inhomogeneity, to generate the first high-resolution liquid-state NMR spectra acquired at >1 GHz. 相似文献
992.
A question of some interest in computational statistical mechanics is whether macroscopic quantities can be accurately computed without detailed resolution of the fastest scales in the problem. To address this question a simple model for a distinguished particle immersed in a heat bath is studied (due to Ford and Kac). The model yields a Hamiltonian system of dimension 2N+2 for the distinguished particle and the degrees of freedom describing the bath. It is proven that, in the limit of an infinite number of particles in the heat bath (N), the motion of the distinguished particle is governed by a stochastic differential equation (SDE) of dimension 2. Numerical experiments are then conducted on the Hamiltonian system of dimension 2N+2 (N1) to investigate whether the motion of the distinguished particle is accurately computed (i.e., whether it is close to the solution of the SDE) when the time step is small relative to the natural time scale of the distinguished particle, but the product of the fastest frequency in the heat bath and the time step is not small—the underresolved regime in which many computations are performed. It is shown that certain methods accurately compute the limiting behavior of the distinguished particle, while others do not. Those that do not are shown to compute a different, incorrect, macroscopic limit. 相似文献
993.
Abe H Matsumoto F Alden LR Warren SC Abruña HD DiSalvo FJ 《Journal of the American Chemical Society》2008,130(16):5452-5458
A Pt-based electrocatalyst for direct fuel cells, Pt3Ti, has been prepared in the form of nanoparticles. Pt(1,5-cyclooctadiene)Cl2 and Ti(tetrahydrofuran)2Cl4 are reduced by sodium naphthalide in tetrahydrofuran to form atomically disordered Pt3Ti nanoparticles (FCC-type structure: Fm3m; a = 0.39 nm; particle size = 3 +/- 0.4 nm). These atomically disordered Pt3Ti nanoparticles are transformed to larger atomically ordered Pt3Ti nanoparticles (Cu3Au-type structure: Pm3m; a = 0.3898 nm; particle size = 37 +/- 23 nm) by annealing above 400 degrees C. Both atomically disordered and ordered Pt3Ti nanoparticles show lower onset potentials for the oxidation of formic acid and methanol than either pure Pt or Pt-Ru nanoparticles. Both atomically disordered and ordered Pt3Ti nanoparticles show a much lower affinity for CO adsorption than either pure Pt or Pt-Ru nanoparticles. Atomically ordered Pt3Ti nanoparticles show higher oxidation current densities for both formic acid and methanol than pure Pt, Pt-Ru, or atomically disordered Pt3Ti nanoparticles. Pt3Ti nanoparticles, in particular the atomically ordered materials, have promise as anode catalysts for direct fuel cells. 相似文献
994.
The reaction of phosphonium alkylidenes [(H2IMes)RuCl2=CHPR3]+[A]- (R = C6H11, A = OTf or B(C6F5)4, 1-Cy; R = i-C3H7, A = ClB(C6F5)3 or OTf, 1-iPr) with 1 equiv of ethylene at -78 degrees C, in the presence of 2-3 equiv of a trapping olefin substrate, yields intermediates relevant to olefin metathesis catalytic cycles. Dimethyl cyclopent-3-ene-1,1-dicarboxylate gives solutions of a substituted ruthenacyclobutane 3 of relevance to ring closing metathesis catalysis. 1H and 13C NMR data are fully consistent with its assignment as a ruthenacyclobutane, but 1JCC values of 23 Hz for the CalphaH2-Cbeta bond and 8.5 Hz for the CalphaH-Cbeta bond point to an unsymmetrical structure in which the latter bond is more activated than the former. In contrast, trapping with acenaphthylene leads to an olefin carbene complex (6) in which the putative ruthenacyclobutane has opened; this species was also fully characterized by NMR spectroscopy and compared to related species reported previously. 相似文献
995.
Inflammasomes are multiprotein complexes formed to regulate the maturation of pro-inflammatory caspases, in response to intracellular or extracellular stimulants. Accumulating studies showed that the inflammasomes are implicated in the pathogenesis of inflammatory bowel disease (IBD), although their activation is not a decisive factor for the development of IBD. Inflammasomes and related cytokines play an important role in the maintenance of gut immune homeostasis, while its overactivation might induce excess immune responses and consequently cause tissue damage in the gut. Emerging studies provide evidence that some genetic abnormalities might induce enhanced NLRP3 inflammasome activation and cause colitis. In these cases, the colonic inflammation can be ameliorated by blocking NLRP3 activation or its downstream cytokine IL-1β. A number of natural products were shown to play a role in preventing colon inflammation in various experimental colitis models. On the other hand, lack of inflammasome function also causes intestinal abnormalities. Thus, an appropriate regulation of inflammasomes might be a promising therapeutic strategy for IBD intervention. This review aims at summarizing the main findings in these studies and provide an outline for further studies that might contribute to our understanding of the role of inflammasomes in the pathogenesis and therapeutic treatment of IBD. 相似文献
996.
Warren Shrader 《Acta Analytica》2008,23(3):257-271
This paper is an investigation into the nature of physicalism as well as to the possibility of formulating physicalism as
a supervenience thesis. First, I review the motivation for finding a supervenience thesis that characterizes physicalism.
Second, I briefly survey the types of supervenience theses that have been proposed as necessary (or, in some cases, as necessary
and sufficient) for physicalism. Third, I analyze the recent supervenience thesis proposed by Frank Jackson and expounded
upon by Gene Witmer. Jackson claims the supervenience thesis is both necessary and sufficient for physicalism; Witmer has
proposed a different interpretation of one of the Jackson’s key notions and has suggested an amended supervenience thesis
that is, if not sufficient, at least necessary for physicalism. However, I will argue that neither Jackson’s nor Witmer’s
supervenience theses as stated are necessary for physicalism.
相似文献
Warren ShraderEmail: |
997.
P. P. Bachelor J. I. Friese C. E. Aalseth J. I. McIntyre H. S. Miley R. W. Perkins G. A. Warren 《Journal of Radioanalytical and Nuclear Chemistry》2008,276(2):363-367
In anticipation of a nuclear detonation, techniques to quickly assess the radiation exposure of evacuees should be developed.
Based on experience relating neutron radiation exposures to activation products, measurement of activation products can be
performed in a few minutes. Personal items exposed to significant levels of radiation allows neutron dose assessment via the
activation products. This approach allows prompt collection of important data on human exposure following a nuclear attack.
Data collected will facilitate triage decisions for emergency medical treatment to ameliorate the radiation effects on exposed
individuals. Activation experiments with everyday items exposed to a neutron source are presented. 相似文献
998.
The binding energies of the p-, m-, and o-difluorobenzene-H(2)O complexes have been measured by velocity map ion imaging to be 922+/-10, 945+/-10, and 891+/-4 cm(-1), respectively. The lack of variation provides circumstantial evidence for water binding to the three isomers via the same interaction, viz. an in-plane O-H...F hydrogen bond to one of the fluorine atoms on the ring, with a second, weaker interaction of the water O atom with an ortho hydrogen, as determined previously for the p-difluorobenzene-H(2)O complex [Kang et al., J. Phys. Chem. A 109, 767 (2005)]. The ground state binding energies for the difluorobenzene-H(2)O complexes are approximately 5%-11% larger than that for benzene-H(2)O, where binding occurs to the pi electrons out-of-plane. However, in the S(1) state the binding energies of the o- and p-difluorobenzene-H(2)O complexes are smaller than the benzene-H(2)O value, raising an interesting question about whether the geometry at the global energy minimum remains in-plane in the excited electronic states of these two complexes. Recoil energy distributions for dissociation of p-difluorobenzene-H(2)O have been measured from the 3(1), 5(2), and 3(1)5(1) levels of the excited electronic state. These levels are 490, 880, and 1304 cm(-1), respectively, above the dissociation threshold. Within the experimental uncertainty, the recoil energy distributions are the same for dissociation from these three states, with average recoil energies of approximately 100 cm(-1). These recoil energies are 60% larger than was observed for the dissociation of p-difluorobenzene-Ar, which is a substantially smaller increase than the 400% seen in a comparable study of dissociation within the triplet state for pyrazine-Ar, -H(2)O complexes. The majority of the available energy is partitioned into vibration and rotation of the fragments. 相似文献
999.
A general approach is presented for spatially coarse-graining lattice kinetic Monte Carlo (LKMC) simulations of systems containing strongly interacting particles. While previous work has relied on approximations that are valid in the limit of weak interactions, here we show that it is possible to compute coarse-grained transition rates for strongly interacting systems without a large computational burden. A two-dimensional square lattice is employed on which a collection of (supersaturated) strongly interacting particles is allowed to reversibly evolve into clusters. A detailed analysis is presented of the various approximations applied in LKMC coarse graining, and a number of numerical closure rules are contrasted and compared. In each case, the overall cluster size distribution and individual cluster structures are used to assess the accuracy of the coarse-graining approach. The resulting closure approach is shown to provide an excellent coarse-grained representation of the systems considered in this study. 相似文献
1000.