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61.
62.
The triphenylallenyl cation (8), generated from triphenylpropynol (7) and FSO3H, reacts with alkenes to give the allyl cations 12, which may be deprotonated to yield the methyleneccylobutenes 14. Alternatively, 12 can be converted into the 2-vinyl-indenes 13 two subsequent electrocyclic reactions. 相似文献
63.
Gerhard Cordier Christoph Schwidetzky Herbert Schäfer 《Journal of solid state chemistry》1984,54(1):84-88
The new compound BaSb2S4 crystallizes in the monoclinic system (space group: , No. 14) with a = 8.985(2) Å, b = 8.203(3) Å, c = 20.602(5) Å, β = 101.36(3)°. SbS3 ψ tetrahedra and ψ-trigonal SbS4 bipyramids are connected by common corners and edgers to infinite strings. These are arraged cross-wise in sheets perpendicular to the c axis. 相似文献
64.
The generation of thiirenes in the thermal and photochemical nitrogen elimination of 1,2,3-thiadiazoles is discussed in relation to oxirene formation. Isotope labelling experiments were performed with 4-phenyl-[4-13C]-1,2,3-thiadiazole ( 7 ) as the substrate. 相似文献
65.
Herbert Cadosch Ulrich Vgeli Peter Rüedi Conrad Hans Eugster 《Helvetica chimica acta》1978,61(2):783-794
On the Carotenoids Flavoxanthin and Chrysanthemaxanthin: 1H-NMR., 13C-NMR. and Mass Spectra, Absolute Configuration, Survey of Published Data Very pure flavoxanthin ( 1 ) and chrysanthemaxanthin ( 2 ) have been reisolated from flower heads of Taraxacum officinale. Both compounds were characterized by chromatographic, chemical and chiroptical data and extensive NMR. measurements. Examination of many published data on 1 and 2 led to the conclusion that flavoxanthin has often been mistaken for chrysanthemaxanthin and vice versa. Chemical degradation of 1 and 2 to (?)-loliolide ( 5 ) coupled with NMR. evidence (ASIS, spin-decoupling, NOE) allowed the assignment of the absolute configurations of 1 and 2 . Thus (+)-flavoxanthin is (3S,5R,8R, 3′R,6′R)-5, 8-epoxy-5, 8-dihydro-β, ε-carotene-3, 3′-diol and (+)-chrysanthemaxanthin its C(8)-epimer. 相似文献
66.
William T. Speck Amy J. Behrman Pnina G. Rosenkranz Doria Gordon Herbert S. Rosenkranz 《Photochemistry and photobiology》1980,31(5):513-517
Abstract— The unfertilized oocytes and spermatozoa of the American sea urchin ( Arbacia punctulata ) were exposed to phototherapy lights in order to determine the effect of this treatment regimen on post-irradiation fertilization and embryonic development. Light treatment revealed dose-dependent abnormalities in fertilization and subsequent embryonic development. 相似文献
67.
Herbert W. Zimmermann 《Angewandte Chemie (International ed. in English)》1986,25(2):115-130
Ethidium and acridine dyes are classical model substances for studying the binding of small, pharmacologically active molecules to DNA. Intercalation between the DNA base pairs is nearly always proposed as the most important type of binding. According to our investigations, however, there is a second type of binding, which also occurs when the concentration of the bound molecules is low and will be referred to here as external or preintercalative binding. The experimental binding isotherms show that the binding constant for intercalation KS1 is considerably smaller than that for external binding KS2 (KS1 > KS2). This surprising result is not due to the binding enthalpy (ΔH ≈ ΔH) but to the binding entropy (ΔS > ΔS). Electrostatic interactions between the dye and the DNA represent the most important contribution to both types of binding; they are supplemented by hydrogen bonds and hydrophobic interactions. The behavior of a substance in living cells, however, cannot be reliably predicted from its in vitro binding to DNA. Very few substances are bound to the DNA of the nuclear chromatin in cell culture; for example, dyes often accumulate instead in the lysosomes. In some cases the dye binds specifically and very efficiently to the mitochondria of the living cell, especially to the mitochondrial membranes, the sites of oxidative phosphorylation. 相似文献
68.
69.
A very simple model for a seven-membered ring having fixed bond lengths and fixed ring bond angles is presented. The model pseudorotates in both the twist-chair/chair and the twist-boat/boat conformations and gives reasonably accurate detailed geometries. 相似文献
70.
Ofial AR Ohkubo K Fukuzumi S Lucius R Mayr H 《Journal of the American Chemical Society》2003,125(36):10906-10912
Second-harmonic alternating current voltammetry has been used to determine one-electron reduction potentials of 15 diarylcarbenium ions and 5 structurally analogous quinone methides, which have been employed as reference electrophiles for the development of nucleophilicity scales. A linear correlation (r(2) = 0.993) between the empirical electrophilicity parameters E and the reduction potentials in acetonitrile (E = 14.091E degrees (red) - 0.279) covering a range of 1.64 V (or 158 kJ mol(-)(1)) has been observed. For a large number of nucleophiles, it has been demonstrated that the observed activation free energies of the electrophile-nucleophile combinations are 61-195 kJ mol(-)(1) smaller than the free energy change of electron transfer from nucleophile to electrophile, which definitely excludes outer-sphere electron transfer occurring during these reactions. 相似文献