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21.
A semi-empirical calculation (PM3) was applied to elucidate the anodic oxidation mechanism of N,N-dimethylaniline (DMA) and the dimerization of a cation radical (A) derived from DMA was ruled out. The heat of reaction value of the dimerization of A was 42.43 kcal/mol. We propose the following. Cation radical A reacts with DMA to generate another cation radical (D). This reaction was exothermic and the heat of reaction value and the activation energy were -0.35 kcal/mol and 1.31 kcal/mol, respectively. Deprotonation of D by DMA gives neutral radical (E), which is oxidized to TMB by A. All these reactions were exothermic. 相似文献
22.
A new and simple method to expand the anharmonic vibrational wave functions with respect to the harmonic oscillator wave functions is proposed. The coefficients of the expansion are given as matrix elements of the S function of the contact transformation in the perturbation theory and the explicit expressions of these coefficients are given within the approximation to the second order in λ. As an example of the expansion, the wave functions of water molecules were calculated and applied to the calculation of infrared band intensities and average values of dipole moments in several states. 相似文献
23.
24.
A simple anharmonic potential containing 18 quadratic, 6 cubic, and 6 quartic constants is proposed to fit 124 vibrational frequencies of 1,1-dichloroethylene and its 37Cl isotope in the region from 10 000 to 350 cm?1. The level patterns in the first and the second overtone regions of the CH2 stretching vibrations are explained by the absence of large higher-order interaction terms between the two CH stretching coordinates. 相似文献
25.
Allylation and propargylation of glyoxylic oxime ether in the presence of a catalytic amount of palladium(0) complex and indium(I) iodide were studied. Excellent diastereoselectivities in allylation were achieved in the presence of water, although low diastereoselectivities were observed in the absence of water. Propargylation of glyoxylic oxime ether proceeded with good diastereoselectivities in the presence of LiBr or LiCl. 相似文献
26.
Makoto Yamaoka 《Tetrahedron letters》2009,50(27):3849-3154
Stereocontrolled synthesis of a fully functionalized AB ring moiety of fomitellic acids was accomplished. The tricyclic skeleton was stereoselectively constructed by means of titanium(III)-mediated radical cascade cyclization of epoxypolyene. The stereochemistry at C1 and C3 was controlled by a vinylogous Mukaiyama aldol reaction and a Sharpless asymmetric epoxidation, respectively. 相似文献
27.
Makoto Yamaoka 《Tetrahedron letters》2010,51(2):287-8779
A remarkable enhancement in the rate of a TiCl4-mediated stereoselective vinylogous Mukaiyama aldol reaction (VMAR) using vinylketene silyl N,O-acetal 1 was observed in the presence of water. 相似文献
28.
Spectroscopic measurements of excited particles in a N2 gas RF plasma-assisted carbon laser ablation
M.A. Bratescu N. Sakura D. Yamaoka Y. Sakai H. Sugawara Y. Suda 《Applied Physics A: Materials Science & Processing》2004,79(4-6):1083-1088
In this work, we investigated a carbon plasma plume produced by laser ablation of a graphite target in a nitrogen gas environment. The spatial distributions of C and N atoms were measured by time-resolved absorption spectroscopy. The spatial distributions of the relative densities of CN radicals, C2, and C3 molecules were measured using time-resolved emission spectroscopy. We determined that nitrogen gas produced an increase in carbon atom and molecule densities in the ablation plume. It was observed that the addition of RF plasma to the plume increased the CN radicals and C atom densities, and decreased the C2 and C3 molecule densities. The RF plasma changed the evolution of various fractional species of C, N, CN, C2, and C3 in the ablation plume. The chemical reactions with and without RF plasma were explained using the evolution and density of the fractional species of C, N, CN, C2, and C3in the plume. PACS 52.38.Mf; 42.62.Fi; 33.20.-t; 81.05.Uw 相似文献
29.
A nonlinear curve fitting program MULTI(FILT) into which the fast inverse Laplace transform (FILT) is incorporated was developed on a microcomputer. FILT is an algorithm for the numerical inversion of Laplace-transformed equations (image equations) to generate the corresponding real time courses. The pharmacokinetic models can be defined in the form of Laplace-transformed equations as a subroutine in MULTI(FILT). MULTI(FILT) achieves the numerical inversion of the defined image equations according to FILT and the subsequent curve-fitting of the inverse-transformed time courses to the experimental data points to estimate the pharmacokinetic parameters by the nonlinear least-squares method. MULTI(FILT) has a function to impose constraints on the pharmacokinetic parameters. In order to verify the reliability of MULTI(FILT), the pharmacokinetic parameters estimated by MULTI(FILT) were compared with those by MULTI using 100 time courses which were artificially generated according to the Monte Carlo method, based on data for theophylline and bishydroxycoumarin. The estimated pharmacokinetic parameters by MULTI(FILT) agreed with those by MULTI. Thus, it is suggested that FILT, developed in the field of electronic technology, is also useful in the pharmacokinetic field. 相似文献
30.
Yukiko IioMakoto Yamaoka Masayoshi JinYoshitaka Nakamura Takahide Nishi 《Tetrahedron: Asymmetry》2011,22(3):323-328
Herein we report the asymmetric synthesis of α,α-disubstituted α-amino alcohol derivatives 22, 25 and 26, key intermediates of a novel immunomodulator, using Seebach’s method. This synthetic method can be applied to the large scale synthesis of chiral sphingosine 1-phosphate-1 (S1P1) receptor agonists, with significant improvements to the previously reported method with regard to the reaction temperature. 相似文献