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81.
82.
Rainer Bachmann Clemens Burda Fabian Gerson Markus Scholz Hans-Jürgen Hansen 《Helvetica chimica acta》1994,77(5):1458-1465
Proton-hyperfine data are reported for the radical anions generated from azulene ( 1 ) and its alkyl derivatives 2 – 11 in 1,2-dimethoxyethane both ‘chemically’ with K and electrolytically. The alkyl derivatives are 1,3-dimethyl- ( 2 ), 5,7-dimethyl- ( 3 ), 1,3,5,7-tetramethyl- ( 4 ), 2-methyl- ( 5 ), 4,6,8-trimethyl- ( 6 ), 2,4,6,8-tetramethyl-( 7 ), 1,3,4,6,8-pentamethyl- ( 8 ), 1,3,4,8-tetramethyl-6-propyl- ( 9 ), 6-(tert-butyl)-1,3,4,8-tetramethyl- ( 10 ), and 1,2,3,4,6,8-hexamethylazulene ( 11 ). Alkyl substituents at the odd-numbered centers μ = 1, 3, 5, and 7 partly shift the π-spin population from the seven- to the five-membered ring, whereas those at the even-numbered centers μ = 4, 6, and 8 exert an opposite effect on the π-spin distribution. 相似文献
83.
84.
Gil Zilber Vladimir Rozenshtein Ari Ayalon Haim Levanon Mordecal Rabinovitz Lawrence T. Scott Hope B. Warren Gaby Persy Jakob Wirz 《Research on Chemical Intermediates》1996,22(9):839-854
Five reaction stages have been identified in the reduction of pyracylene to its dianion. The same stages were also observed in the photochemical oxidation starting with the dianion. The formation of dimers of anions and of mixed valence aggregates is discussed. 相似文献
85.
Dielectrometry is used as a novel technique for following the rate of a Friedel-Crafts alkylation reaction in supercritical (sc) difluoromethane. Although the process was not optimized, good product yields were obtained and reaction rates were found to be larger than in CO2 at comparable conditions. The reaction order is determined using the initial rate method and the reaction is shown to be first-order with respect to both anisole and t-butyl chloride. The reaction rate constant is unaffected by pressures above 120 bar but close to the critical pressure the value decreases with increasing pressure. It is also shown that the product distribution for the alkylation of anisole shows significant pressure dependence with substitution at the ortho-position being favored at lower pressures, which is ascribed to hydrogen bonding. This pressure dependency is not observed in sc CO2 or using toluene as a substrate, which supports the idea that hydrogen bonding may be important in the reaction mechanism. The effect of the different reagents and temperature on the rate of the alkylation reaction was also determined. 相似文献
86.
M.C. Grossel A.K. Cheetham D.A.O. Hope K.P. Lam M.J. Perkins 《Tetrahedron letters》1979,20(15):1351-1354
X-ray crystallographic and solution 1H n.m.r. studies of -1,4-dihydro-4-tritylbiphenyl (2) both suggest the presence of an almost planar cyclohexa-1,4-diene ring (αmean = 1975°).4 相似文献
87.
ESR.-spectra are reported for the radical anion I · Θ of 2,7-diazapyrene (I), along with those for the radical cations I(2H) · ⊕ and I(2 CH3) · ⊕ of 2,7-dihydro-2,7-diazapyrene and its 2,7-dimethyl-derivative, respectively. In contrast to the analogous radical ions of 4,4′-bipyridyl (II) and other previously studied diazaaromatic compounds, there is a striking change in the 14N and proton coupling constants on going from the radical anion I · Θ to the radical cations I(2H) · ⊕ and I(2 CH3) · ⊕. This change can be rationalized in terms of the HMO model of the pyrene π-system. A reversal in the energy sequence of the lowest antibonding orbitals is predicted upon an increase in the absolute value of the Coulomb integral for the azasubstituted π-centres, such an increase simulating the enhanced electronegativity of the azanitrogen atoms 2 and 7 on protonation. 相似文献
88.
ESR. data are reported for the radical anions (II? to VI?) of five alkyl substituted 6a-thiathiophthenes. Rates and activation parameters for the inversion of the 3,4-trimethylene chain in IV?, V? and VI? have been obtained by means of an iterative least squares computer program ESRCEX. Preferential conformations of the alkyl substituents are discussed in terms of the 〈cos2θ〉 dependence of the β-proton coupling constants and with the aid of molecular models. Experimental evidence strongly suggests that the partial rotation of the ethyl and isopropyl groups in V? and VI? is correlated with the inversion of the 3,4-trimethylene chain. 相似文献
89.
In this study, a continuous linear alcohol derivatization is developed. Reaction of alcohol group (ROH) with benzoyl chloride (BC) is carried out in an on-line system with UV detection. All reaction conditions, as flow rate (FR), ROH/BC molar ratio, wavelength, temperature, microwave (MW) irradiation and reaction coil size (internal diameter and length) were optimized. 0.5 mL min−1, 2.49 [BC]/[ROH], 230 nm, 60 °C or medium power (225 W) when MW irradiation was used and a reactor coil of 159 μL (0.5 mm × 810 mm) were the optimum conditions. The on-line system with microwave irradiation was more efficient than the one with a water bath heating. The developed system reduces analysis time consumption, reagent amounts and this system was used to evaluate the composition of commercial samples of alcohols polyethoxylated (surfactants). 相似文献
90.
Fabian Gerson Ren Heckendorn Reinhart Mckel Fritz Vgtle 《Helvetica chimica acta》1985,68(7):1923-1932
The radical anions of 1,8-diphenylnaphthalene ( 1 ) and its decadeuterio-(D10- 1 ) and dimethyl-( 2 ) derivatives, as well as those of [2.0.0] (1,4)benzeno(1,8)naphthaleno(1,4)benzenophane ( 3 ) and its olefinic analogue ( 4 ) have been studied by ESR and ENDOR spectroscopy, At a variance with a previous report, the spin population in \documentclass{article}\pagestyle{empty}\begin{document}$ \rm {1}^{-\kern-4pt {.}} $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \rm {2}^{-\kern-4pt {.}} $\end{document} is to a great extent localized in the naphthalene moiety. A similar spin distribution is found for \documentclass{article}\pagestyle{empty}\begin{document}$ \rm {3}^{-\kern-4pt {.}} $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \rm {4}^{-\kern-4pt {.}} $\end{document}. The ground conformations of \documentclass{article}\pagestyle{empty}\begin{document}$ \rm {1}^{-\kern-4pt {.}} $\end{document}-\documentclass{article}\pagestyle{empty}\begin{document}$ \rm {4}^{-\kern-4pt {.}} $\end{document} are chiral of C2 symmetry. For \documentclass{article}\pagestyle{empty}\begin{document}$ \rm {1}^{-\kern-4pt {.}} $\end{document}, an energy barrier between these conformations and the angle of twist about the bonds linking the naphthalene moiety with the phenyl substituents were estimated as ca. 50 kJ/mol and ca. 45°, respectively. The radical trianions of 1 , D10- 1 , and 2 , have also been characterized by their hyperfine data. In \documentclass{article}\pagestyle{empty}\begin{document}$ \rm {1}^{3-\kern-4pt {.}} $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \rm {2}^{3-\kern-4pt {.}} $\end{document}, the bulk of the spin population resides in the two benzene rings so that these radical trianions can be regarded as the radical anions of ‘open-chain cyclophanes’ with a fused naphthalene π-system bearing almost two negative charges. The main features of the spin distribution in both \documentclass{article}\pagestyle{empty}\begin{document}$ \rm {1}^{-\kern-4pt {.}} $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \rm {1}^{3-\kern-4pt {.}} $\end{document} are correctly predicted by an HMO model of 1 . 相似文献