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91.
D. T. Clark M. Z. Abrahman 《Journal of polymer science. Part A, Polymer chemistry》1981,19(11):2689-2703
A systematic investigation has been made of the composition, gross structural features, and rates of deposition of plasma polymer films produced from the excitation of inductively coupled RF plasmas in the isomeric tetrafluorobenzenes. ESCA data reveal that the dominant reaction involves rearrangement such that under a wide variety of experimental conditions the composition of the crosslinked products remains essentially the same as that of the starting material. Small differences in rates of deposition are observed for the different isomers, and theoretical SCF MO studies at the MNDO level provides a basis for discussion of the experimental data. 相似文献
92.
D. T. Clark B. J. Cromarty A. Dilks 《Journal of polymer science. Part A, Polymer chemistry》1978,16(12):3173-3184
Nonempirical LCAO MO SCF computations (in the ΔSCF formalism) have been carried out of binding energies and relaxation energies for an extensive series of oxygen-containing organic systems encompassing most of the common functionalities. The molecules for which experimental data are available for comparison demonstrate the adequacy of the treatment for describing the relative binding energies for both the Cls and Ols core levels. A sound basis is therefore provided for the discussion of relative core binding energies (Cls and Ols) for functionalities for which experimental data are not available, that is, hydroperoxides, peroxides, peroxyacids, and peroxyesters, a knowledge of which is essential for investigations of the surface oxidation of polymers by means of ESCA. Cls shifts are discussed in terms of primary and secondary substituent effects of oxygen, which greatly simplify the analysis of complex unresolved spectra, whereas for the Ols levels a similar but less straightforward situation exists. The relaxation energies associated with both Cls and Ols core ionization follow a dependence on the binding energy for a given structural type. 相似文献
93.
94.
在氧离子导体La2Mo1.7W0.3O9的基础上,采用固相法合成了La位掺杂的Ca系列新型氧化物La2-xCaxMo1.7W0.3O9-δ(0≤x≤0.2)。通过XRD、Raman和XPS等手段对化合物结构进行表征,交流阻抗谱测试其电性能。结果表明:掺杂离子Ca2+的半径小于基质离子La3+的半径导致晶格收缩;Ca的掺杂在La2Mo1.7W0.3O9自身内置氧空位的基础上增加了额外的氧空位,提高了氧离子导体的电导率,550 ℃电导率由0.79 × 10-4 S·cm-1 (x=0.0)增加到1.5 × 10-4 S·cm-1 (x=0.16,0.2),电导率增加89.9%。 相似文献
95.
W.John Albery David Clark Humphrey J.J. Drummond Anthony J.M. Coombs William K. Young Clive E.W. Hahn 《Journal of Electroanalytical Chemistry》1992,340(1-2)
A novel electrochemical sensor for the determination of CO2 in expired breath is described. The sensor works by generating
from the reduction of O2 in dimethyl sulphoxide (DMSO) in a generating pulse. There is a rapid titration reaction between the
and any CO2 present. In the recovery pulse the amount of unreacted
is determined. The larger the concentration of CO2 the less
is found in the recovery pulse. The solubilities and diffusion coefficients of O2 and CO2 in DMSO have been determined using rotating disc voltammetry and rotation speed step experiments. The stoichiometry, the product, and the rate constant of the titration reaction have been determined using ring—disc voltammetry and laser Raman spectroscopy. The operation and the effect of adventitious water on the sensor are described. Results are presented which show that the sensor can indeed measure the breath-by-breath rhythm of expired CO2 from a human subject. 相似文献
96.
Clark GR Pytel PD Squire CJ Neidle S 《Journal of the American Chemical Society》2003,125(14):4066-4067
The first crystal structure of a drug (daunomycin) bound to a parallel-stranded intermolecular telomeric G4 quadruplex (d(TGGGGT)4) has been determined to high resolution. A planar assemblage of three daunomycin molecules stacks onto the 5' end of the G4 column, with the daunosamine substituents occupying three of the four quadruplex grooves. The surface area of the terminal G-quartet in this parallel DNA quadruplex, presently occupied by three daunomycins, is sufficiently large that it could easily accommodate other potential telomerase inhibitors such as substituted porphyrins or telomestatin. 相似文献
97.
Samuel M. Blau Hetal D. Patel Evan Walter Clark Spotte-Smith Xiaowei Xie Shyam Dwaraknath Kristin A. Persson 《Chemical science》2021,12(13):4931
Modeling reactivity with chemical reaction networks could yield fundamental mechanistic understanding that would expedite the development of processes and technologies for energy storage, medicine, catalysis, and more. Thus far, reaction networks have been limited in size by chemically inconsistent graph representations of multi-reactant reactions (e.g. A + B → C) that cannot enforce stoichiometric constraints, precluding the use of optimized shortest-path algorithms. Here, we report a chemically consistent graph architecture that overcomes these limitations using a novel multi-reactant representation and iterative cost-solving procedure. Our approach enables the identification of all low-cost pathways to desired products in massive reaction networks containing reactions of any stoichiometry, allowing for the investigation of vastly more complex systems than previously possible. Leveraging our architecture, we construct the first ever electrochemical reaction network from first-principles thermodynamic calculations to describe the formation of the Li-ion solid electrolyte interphase (SEI), which is critical for passivation of the negative electrode. Using this network comprised of nearly 6000 species and 4.5 million reactions, we interrogate the formation of a key SEI component, lithium ethylene dicarbonate. We automatically identify previously proposed mechanisms as well as multiple novel pathways containing counter-intuitive reactions that have not, to our knowledge, been reported in the literature. We envision that our framework and data-driven methodology will facilitate efforts to engineer the composition-related properties of the SEI – or of any complex chemical process – through selective control of reactivity.A chemically consistent graph architecture enables autonomous identification of novel solid-electrolyte interphase formation pathways from a massive reaction network. 相似文献
98.
The source of the effect of N-alkylation on the redox properties of Ni(II/I) and Cr(III/II) cyclam complexes has been investigated using DFT calculations. The structures of the anhydrous and hydrated complexes were optimized in the gas phase, and single point calculations were performed in a polarized continuum. The main results are the following: the decrease in outer sphere solvation upon N-alkylation is the major source of the relative stabilization of the lower oxidation state complexes by the tertiary amine ligands; tertiary amine nitrogen donors are stronger sigma-donors than the secondary amines, as predicted from the inductive effect of alkyls; steric strain elongates the metal-nitrogen bonds in the tertiary complexes and decreases the ligand strain energies; and the site of water binding to the complexes differs because of their different electronic structures (i.e., in the Ni complexes, the water molecules bind to the M[bond]N[bond]H sites, whereas in the Cr complexes they bind to the central metal cation). Outer sphere hydrogen bonding of water to the ligands in the coordination sphere lowers the ionization potentials by charge delocalization. 相似文献
99.
A High-Order Finite Difference Scheme for 3D Unsteady Convection Diffusion Reaction Equations北大核心CSCD
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针对三维非稳态对流扩散反应方程,构造了一种高精度紧致有限差分格式,对空间的离散采用四阶紧致差分方法,对时间的离散采用Taylor级数展开和余项修正技术,所提格式在时间上的精度为二阶、在空间上的精度为四阶。利用Fourier稳定性分析法证明了该格式是无条件稳定的。最后给出数值算例验证了理论结果。 相似文献
100.
为解决供应链系统中信息时滞和不对称问题,加快推动区块链技术在供应链管理中的创新发展,本文运用控制理论构建由分销商和零售商组成的二级供应链系统控制模型,引入区块链技术影响下的信息校正因子,推导系统的传递函数,通过MATLAB仿真不同需求信号下的订单可变性和库存波动。仿真结果表明:(1)区块链技术的应用提高了库存系统的精准性和稳定性;(2)高库存可变性伴随着高订单可变性;(3)指数平滑系数和区块链技术影响下的信息校正因子有效抑制供应链中的牛鞭效应;(4)信息延迟时间越长,区块链技术影响下的信息校正因子对控制系统的抑制作用越显著。本研究量化了区块链技术对供应链中牛鞭效应的影响,提高了供应链系统的精准性和稳定性,丰富了区块链技术在供应链管理中的应用,为企业管理者提供新的研究思路。 相似文献