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71.
The mechanism of second H2O formation in fully reduced cytochrome c oxidase is examined by sequential additions of one electron and two protons to a [Fe(IV)O, Cu(II)] compound II, which is the final intermediate of first H2O formation. It is found that the addition of one electron induces the concerted proton–electron transfer from the CuB to FeO moieties with no energy barriers. The H2O molecule coordinating to the Cu atom is a key molecule for the proton transfer from the CuB moiety to the FeO and/or Fe–OH moieties. It is also found from the results in previous and the present works that one can realize the reduction process of dioxygen by fully reduced cytochrome c oxidase. 相似文献
72.
The indium hydride generated from NaBH4 and InCl3, is a promising candidate of alternative to Bu3SnH. In particular, the catalytic performance of InCl3 in the dehalogenation of alkyl and aryl halides, intramolecular cyclization and intermolecular coupling reaction are noteworthy. 相似文献
73.
Yoshiyuki Kawase Seiji Yamaguchi Osamu Maeda Akemi Hayashi Ichihiro Hayashi Kazuko Tabata Masako Kondo 《Journal of heterocyclic chemistry》1979,16(3):487-491
Benzofuro[2,3-b]quinoline ( Ia ) and its 11-methyl derivative ( Ib ) were synthesized by demethylcyclization of 3-(o-methoxyphenyl)-1,2-dihydroquinolin-2-ones (VIa,b). Benzofuro[2,3-b]quinoline-11-carboxylic acid (Id) was synthesized by chlorination followed by the action of potassium hydroxide of a lactone (IX) prepared by demethyl-cyclization of 3-(o-methoxyphenyl)-2-oxo-1,2-dihydroquinoline-4-carboxylic acid (VIII). Isomeric benzofuro[3,2-c]quinoline (Ha) and its 6-methyl derivative (IIb) were synthesized by demethyl-cyclization of 3-(o-methoxyphenyl)-1,4-dihydroquinolin-4-ones (XIa,b). Both the methyl derivatives (Ib and IIb) were converted to the carboxylic acids (Id and IId) through condensation with benzaldehyde followed by oxidation. The benzofuroquinolines (Ia,b,d and IIa,b) thus obtained were oxidized to the corresponding N-oxides (IIIa,b,d and IVa,b). 相似文献
74.
Katsuo Mitani Toshimitsu Suzuki Akihiro Matsuo Yoshinobu Takegami 《Journal of polymer science. Part A, Polymer chemistry》1974,12(4):771-784
The 220-MHz proton magnetic resonance and infrared spectra of stereoregular polypropylenes polymerized with a number of Ziegler-Natta catalysts and isotactic polymers of low molecular weight obtained by thermal degradation of a highly isotactic polypropylene were measured in an attempt to obtain some information on the local regularity. The fraction of thermally degraded polymer soluble in diethyl ether shows stereorandomness (tactie sequence length is quite short), and the portion soluble in n-pentane has stereoblock character. The results so obtained provide strong evidence that racemic dyads of whole polymer consist of two models of racemic dyad isolated and racemic dyads in groups. The polymers prepared with vanadium catalyst systems show stereorandom character and these polymers have \documentclass{article}\pagestyle{empty}\begin{document}$\hbox{-\hskip-1pt-}\hskip-4pt({\rm CH}_2 \rlap{--} )$\end{document} groups formed by two propylene units in a tail-to-tail linkage. Syndiotactic polypropylene has head-to-head and tail-to-tail arrangements of two propylene units and this is the origin of randomness of syndiotacticity. 相似文献
75.
Syndiospecific living propylene polymerization catalyzed by titanium complexes having fluorine-containing phenoxy-imine chelate ligands 总被引:3,自引:0,他引:3
Mitani M Furuyama R Mohri J Saito J Ishii S Terao H Nakano T Tanaka H Fujita T 《Journal of the American Chemical Society》2003,125(14):4293-4305
The propylene polymerization behavior of a series of Ti complexes featuring fluorine-containing phenoxy-imine chelate ligands is reported. The Ti complexes combined with methylalumoxane (MAO) can be catalysts for living and, at the same time, stereospecific polymerization of propylene at room temperature or above. DFT calculations suggest that the attractive interaction between a fluorine ortho to the imine nitrogen and a beta-hydrogen of a growing polymer chain is responsible for the achievement of room-temperature living propylene polymerization. Although the Ti complexes possess C(2) symmetry, they are capable of producing highly syndiotactic polypropylenes. (13)C NMR is used to demonstrate that the syndiotacticity is governed by a chain-end control mechanism and that the polymerization is initiated exclusively via 1,2-insertion followed by 2,1-insertion as the principal mode of polymerization. (13)C NMR spectroscopy also elucidated that the polypropylenes produced with the Ti complexes possess regio-block structures. Substitutions on the phenoxy-imine ligands have profound effects on catalytic behavior of the Ti complexes. The steric bulk of the substituent ortho to the phenoxy oxygen plays a decisive role in achieving high syndioselectivity for the chain-end controlled polymerization. Over a temperature range of 0-50 degrees C, Ti complex having a trimethylsilyl group ortho to the phenoxy oxygen forms highly syndiotactic, nearly monodisperse polypropylenes (94-90% rr) with extremely high peak melting temperatures (T(m) = 156-149 degrees C). The polymerization behavior of the Ti complexes can be explained well by the recently proposed site-inversion mechanism for the formation of syndiotactic polypropylene by a Ti complex having a pair of fluorine-containing phenoxy-imine ligands. 相似文献
76.
Shigeru Matsuo Naoto Yakoh Shinji Chino Masahiro Mitani Sanae Tagami 《Journal of polymer science. Part A, Polymer chemistry》1994,32(6):1071-1076
The poly(arylene ether)s were prepared by the nucleophillic aromatic substitution polymerization of phenolphthalin and its derivatives with activated aromatic difluorides. The polymers had glass transition temperatures ranging from 210 to 240°C. Though the monomers have no fluorescence, the resulting polymers fluoresced a light green color in solid and solution states. The maximum excitation and emission wavelengths are 420 nm and 470 nm, respectively. In the polymer solutions, the fluorescence intensity decreased gradually, but the intensity was recovered by heating the polymer at 220°C for a few minutes. The fluorescent polymer had a stable radical. A model compound having the same repeating unit of the polymer was also prepared. The fluorescence properties of this model were almost the same as those of the polymers. © 1994 John Wiley & Sons, Inc. 相似文献
77.
A study by computer simulation is reported of the behavior of a quantized vortex line at a very low temperature when there is continuous excitation of low-frequency Kelvin waves. There is no dissipation except by phonon radiation at a very high frequency. It is shown that nonlinear coupling leads to a net flow of energy to higher wave numbers and to the development of a simple spectrum of Kelvin waves that is insensitive to the strength and frequency of the exciting drive. The results are likely to be relevant to the decay of turbulence in superfluid 4He at very low temperatures. 相似文献
78.
Okubo T Kawajiri R Mitani T Shimoda T 《Journal of the American Chemical Society》2005,127(50):17598-17599
The first mixed-valence coordination polymer indicating ferroelectric properties, {[CuI4CuII(Et2dtc)2Cl3][CuII(Et2dtc)2]2(FeCl4)}n (Et2dtc- = diethyldithiocarbamate), has been synthesized and crystallographically characterized. This complex has a two-dimensional infinite square lattice structure, including both Cu(I) and Cu(II) ions, which is confirmed by XPS and SQUID measurements. In addition, the ferroelectric behaviors are revealed by the dielectric measurements with a LCR meter and a ferroelectric tester. 相似文献
79.