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121.
[structure: see text] The design, synthesis, and biological evaluation of seven totally synthetic analogues of the antitumor agent (+)-discodermolide are reported. Saturation of the terminal diene system, alteration of the substituents on the lactone, and alkylation of the C7-hydroxyl group reveal significant structure-activity relationships. 相似文献
122.
123.
Proteins are continuously synthesized during cell growth and proliferation. At the same time, excessive and misfolded proteins have to be degraded, otherwise they are a burden to cells. Protein degradation is essential to maintain proteostasis in cells, and dysfunction of protein degradation systems results in numerous diseases such as cancer and neurodegenerative diseases. Despite the importance of protein degradation, the degradation pathways of many proteins remain to be explored. Here, we comprehensively investigated the degradation of newly synthesized proteins in human cells by integrating metabolic labeling, click chemistry, and multiplexed proteomics, and systematic and quantitative analysis of newly synthesized proteins first revealed the degradation pathways of many proteins. Bioinformatic analysis demonstrates that proteins degraded through two major pathways have distinct properties and functions. Proteins degraded through the ubiquitin-proteasome pathway contain more disordered structures, whereas those through the autophagy-lysosome pathway have significantly higher hydrophobicity. Systematic and quantitative investigation of the dynamics of newly synthesized proteins provides unprecedented and valuable information about protein degradation, which leads to a better understanding of protein properties and cellular activities.Systematic quantification of the dynamics of newly synthesized proteins first reveals the degradation pathways of many proteins in human cells, and proteins degraded through each of the two major pathways have distinct properties and functions. 相似文献
124.
Redl FX Black CT Papaefthymiou GC Sandstrom RL Yin M Zeng H Murray CB O'Brien SP 《Journal of the American Chemical Society》2004,126(44):14583-14599
We have investigated the structural, magnetic, and electronic properties of nonstoichiometric iron oxide nanocrystals prepared by decomposition of iron(II) and iron(0) precursors in the presence of organic solvents and capping groups. The highly uniform, crystalline, and monodisperse nanocrystals that were produced enabled a full structural and compositional survey by electron microscopy and X-ray diffraction. The complex and metastable behavior of nonstoichiometric iron oxide (wüstite) at the nanoscale was studied by a combination of Mossbauer spectroscopy and magnetic characterization. Deposition from hydrocarbon solvents with subsequent self-assembly of iron oxide nanocrystals into superlattices allowed the preparation of continuous thin films suitable for electronic transport measurements. 相似文献
125.
X. Y. Zhang S. Jin Y. C. Liang Y. F. Ming L. H. Yu M. G. Fan W. F. Wang S. D. Yao 《Research on Chemical Intermediates》1995,21(1):17-24
Photochromic reactions of four indolinospirooxazine derivatives have been studied using nanosecond laser flash photolysis
techniques. Photolysis of the four compounds in acetonitrile and in cyclohexane all leads to the formation of the short-lived
CT intermediates as the predominant photoproducts. In certain circumstances few photomerocyanines (PMC) can be observed. From
the absorption bands and the lifetimes of CT intermediates, it has been speculated that the substituents at the nitrogen atom
of the indole ring influence the structural characteristics of CT intermediates mainly through steric hindrance effects, whereas
the substituents at the 5 position of the indoline ring influence mainly through electron effects. A potential energy surface
model is established to explain the results. 相似文献
126.
Strain energies and resonance energies can be obtained as the energy changes for appropriate homodesmotic reactions using ab initio calculated total energies as the energies of the reactants and products involved. Homodesmotic reactions conserve bond types and preserve valence environments at all atoms, requirements that favor the cancellation of basis set and electron correlation errors in the ab initio energies. In this paper we calculate strain energies and resonance energies for N(4), N(6), and N(8) clusters in a number of chemically significant but, for nitrogen, hypothetical structural forms. The nitrogen cluster strain energies are generally of the same order of magnitude as those of isostructural hydrocarbon clusters, and individual differences can be explained by using the ring strain additivity rule and recognizing the effect of the presence of lone pairs of electrons on nitrogen clusters but not on the hydrocarbons. Resonance energies of the nitrogen clusters are much smaller than those of the comparable aromatic hydrocarbons. The differences can be rationalized by considering the relative strengths of CC and NN single and double bonds. Strain and resonance energies of nitrogen clusters are compared with those previously reported for homoatomic clusters of phosphorus and arsenic. Trends through the series are remarkably similar, but strain energies for clusters from lower periods are progressively smaller. Strain and resonance have been important organizing concepts in organic chemistry for many years. Estimates of corresponding parameters for inorganic analogs are only now becoming available. 相似文献
127.
A stereoselective oxidative free-radical cyclization of beta-keto ester polyenes 7 and 19 has been accomplished as a one-step entry to the tricarbocyclic synthons 8and 21 which contain five and six stereogenic centers, respectively. These key synthons possessing an axial carboethoxy group at C-4 were ultimately converted to the spongian skeleton (8--> 14 and 21 --> 25 -->14). The synthesis of d,l-isospongiadiol (3) from the common intermediate 14 was realized after introduction of the 2alpha-hydroxy group in the spongian A-ring via epoxidation of silyl enol ether 28 and subsequent desilylation. 相似文献
128.
Ming Liao 《Probability Theory and Related Fields》1993,96(2):261-281
Summary We study the asymptotic stability of the stochastic flows on a class of compact spaces induced by a diffusion process in SL(n, R) or GL(n, R). These compact spaces are called boundaries of SL(n, R), which include SO(n), the flag manifold, the sphereS
n–1 and the Grassmannians. The one point motions of these flows are Brownian motions. For almost every, , we determine the set of stable points. This is a random open set whose complement has zero Lebesgue measure. The distance between any two points in the same component of this set tends to zero exponentially fast under the flow. The Lyapunov exponents at stable points are computed explicitly. We apply our results to a stochastic flow onS
n–2 generated by a stochastic differential equation which exhibits some nice symmetry.Research supported in part by Hou Yin Dong Education Foundation of China On leave from Nankai University, Tianjin, China 相似文献
129.
无机材料的微观结构决定了材料的许多特性,如传输行为、催化活性、分离效率、粘附、储存和释放动力学。具有管状结构纳米尺度的材料由于其特殊的结构及由此带来的特殊性能正成为一个令人兴奋的化学研究领域。文章综述了近年来无机纳米管材料的合成途径和进展。 相似文献
130.
A novel molecular probe for identifying properties of supported transitionmetals and metal oxides catalysts was established.The catalytic mechanism oftransition metals was proposed. 相似文献