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  • General Chemistry  (11)
  • Polymer and Materials Science  (10)
  • Sulfoxides  (4)
  • Biochemistry and Biotechnology  (1)
  • Wiley-Blackwell  (22)
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  • Wiley-Blackwell  (22)
  • 1
    ISSN: 0959-8103
    Keywords: anthracene ; fluorescence ; naphthalene ; non-radiative singlet energy transfer ; polyesters ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Steady state fluorescence has been used to study the efficiency of nonradiative single energy transfer for naphthalene → naphthalene and naphthalene → anthracene for polyesters and their bichromophoric model compounds. Polyesters containing only naphthalene groups were derived from 2,6-naphthalene dicarboxylic acid as the rigid unit, and two series of glycols, HO—(CH2)m—OH and HO—(CH2CH2O)n;—OH, where m=2-6 and n=1-4, as flexible spacers. Bichromophoric model compounds were derived from 2-naphthoic acid and the same glycols. In order to study the transfer for naphthalene → anthracene, a first attempt was made by studying bichromophoric model compounds D—(CH2)m—A, where D and A denote 2-naphthoate (donor) and 9-anthranoate (acceptor) groups, respectively. The fluorescence anisotropy measurements in a solid matrix of glassy poly(methyl methacrylate), for the compounds containing only naphthalene groups, and the simple excitation and emission spectra, for the compounds containing naphthalene and antharacene groups, clearly demonstrate the presence of non-radiative singlet-singlet energy transfer, the efficiency of which depends mainly on n (or n). A theoretical treatment using the rotational isomeric state model of the conformatin of these molecules has also been performed. The combination of the experiments and the theoretical analysis establishes that the Förster radii are 1.2 and 1.4 nm for the naphthalene → naphthalene transfer in the bichromophoric model compounds and polyesters, respectively, and 1.6 ± 0.2 nm for the naphthalene → anthracene transfer in the model compounds studied.
    Additional Material: 16 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 47 (1993), S. 1741-1748 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The migration of compounds from polymer-based packaging may impart undesirable odors to foods. We, therefore, undertook a study of the volatile compounds produced during the heating of polyethylene (PE) in the presence of excess O2 at temperatures of 150-350°C and for heating times of 5-15 min. Eightyfour volatile compounds in the range of C5 - C23 were identified by gas chromatography mass spectrometry. The major products were aliphatic hydrocarbons, aldehydes, ketones, and olefins. Changes in temperature and heating times affected the amount and type of compounds produced, with hexanal being found in the largest amount and 300°C resulting in the greatest quantity of volatile compounds. At 350°C, greater amounts and numbers of low-boiling and fewer high-boiling compounds were formed. Only small amounts of volatiles were produced at 150°C. Many of the compounds identified have been reported to have odor and/or toxicological significance. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 62 (1996), S. 375-384 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Glass fibers have been treated with γ-aminopropyl-triethoxysilane (APES) through different silanizating procedures, which include APES aqueous solutions and APES vapor adsorption. Transmission Fourier transform IR (FTIR) measurements have been performed on the silanized samples to characterize the silanization reaction. Dansyl-sulfonamide conjugates have then been formed by reaction of dansyl chloride in dimethylformamide solution with the amine functionality's immobilized on the glass fiber surface. Steady-state and time-resolved fluorescence measurements have been performed on dansylated samples. A dependence of the fluorescence intensity and the wavelength of the maximum emission on the silanization procedure has been observed. Good fits of the fluorescence decays of dansyl labels are found when biexponential functions are used for deconvolution, whereas the decay of dansylamides in fluid solution is single exponential. A two-state model for the solid solvent relaxation seems to apply for this samples. Several surface structural changes produced by the different silanization methods have been proposed. FTIR results support the conclusions drawn from fluorescence measurements. © 1996 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2565-2571 
    ISSN: 1434-193X
    Keywords: Molecular recognition ; Rotaxanes ; Self-assembly ; Template-directed synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three dumbbell-shaped compounds incorporating terminal triisopropylsilyl stoppers, connected to a central 1,5-dioxynaphthalene recognition site by [-CH2CH2O-]n spacers (n = 1-3), have been synthesized. These compounds have been employed as templates for the synthesis of [2]rotaxanes incorporating cyclobis(paraquat-p-phenylene) as the ring component. It was found that the length of the polyether chains of the templates influences the efficiencies of the template-directed syntheses. Rotaxane formation occurs only if n 〉 1 and, when n = 3 the corresponding [2]rotaxane can be isolated in a yield as high as 72 %. This remarkable yield is the highest ever obtained for the template-directed syntheses of [2]rotaxanes incorporating donor/acceptor interactions.
    Additional Material: 4 Ill.
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  • 5
    ISSN: 1434-193X
    Keywords: Fluorine ; Pheromones ; Sulfoxides ; Sulcatol ; Asymmetric synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The pheromone (R)-(-)-sulcatol (10a) and three of its enantiomeric mono-, di-, and trifluoro analogues 10b-d have been synthesized, in six steps and with good overall yields, starting from chiral (R)-2-methyl-5-[(4-methylphenyl)sulfinyl]pent-2-ene (1) and commercially available fluorinated or non-fluorinated acetates.Supporting information for this article is available on the WWW under http://www.wileY-Vch.de/contents/jc_2046/1999/98375_s.pdf or from the author.
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  • 6
    ISSN: 1434-193X
    Keywords: Fluorine ; Lactones ; Annulation ; Ketene ; Sulfoxides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Enantiomerically pure α,α-dichloro β-fluoroalkyl γ-p-tolylthio γ-butyrolactones trans-6a-c have been obtained with excellent stereocontrol (〉 98:2) and enantiomeric purity (〉 98:2) by sulfoxide-directed lactonization (Marino's annu-lation reaction) of β-fluoroalkyl vinyl sulfoxides (R)-(E)-5a-c with dichloroketene. Highly chemoselective dechlorination and desulfurization reactions performed on trans-6c efficiently provided the β-chlorodifluoromethyl γ-butyrolactone (S)-8c, the absolute stereochemistry of which was determined by X-ray diffraction analysis of its γ-p-tolylthio precursor (2R,3S)-7c.
    Additional Material: 1 Ill.
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  • 7
    ISSN: 1434-193X
    Keywords: Fluorinated dideoxynucleosides ; Through-space interactions ; Hydrogen bonds ; Long-range coupling constants ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -A collection of 5′-O-benzyl-2′,3′-dideoxy-4′-(fluoromethyl)nucleosides carrying both purinic and pyrimidinic nucleobases (uracil, 5-Br-uracil, 5-O2N-uracil, 6-Cl-purine and inosine) were synthesized in both the α and the β form. Through-space-transmitted 6JCF NMR coupling constants between F and C-6 (pyrimidinic base) or C-8 (purinic base) were observed for all of the α anomers of the compounds examined, whilst the corresponding 7JHF coupling constants were resolved only for the 5-substituted uracil derivatives. The absolute values of all the through-space couplings were found to decrease monotonically with increasing solvent polarity (CDCl3, MeOD, [D6]acetone, [D6]DMSO). This trend suggests that the through-space interaction is mediated by an intramolecular (sp3)C-F…H-C(sp2) hydrogen bond. The possibility of any relevant solvent-induced conformational change influencing the F/base mutual spatial relationship in the molecules investigated was ruled out by heteronuclear steady-state 1H{19F}-NOE experiments. A linear correlation was observed between 6JCF and 7JHF coupling constants and the Kamlet-Taft's hydrogen bond basicity parameter β. The crystal structures of the α and β anomers of the 5-nitrouracil nucleoside show evidence that the H-6 of the nucleobase forms hydrogen-bond-like interactions involving the O-benzyl oxygen atom in the β anomer, and that in the case of the α anomer this is replaced by the F atom of the fluoromethyl group.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1387-1389 
    ISSN: 1434-193X
    Keywords: Natural products ; Epoxidations ; Asymmetric synthesis ; Fluorine ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The synthesis of enantiomerically and diastereomerically pure (-)-(1R,2R,5R)- and (-)-(1R,2S,5R)-2-fluoro frontalin (7) starting from (+)-(1S)-menthyl-(R)-toluene-4-sulfinate, methylmagnesium bromide, methyl fluoroacetate, 4-pentenyl bromide and diazomethane is described. The absolute stereochemistry was unambiguously determined by X-ray analysis of (+)-(1S,2R,5S,RS)-5, an intermediate in the synthesis of the enantiomeric (+)-(1S,2R,5S)-2-fluoro frontalin (7).
    Additional Material: 2 Ill.
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  • 9
    ISSN: 1434-1948
    Keywords: Silicon ; Silyl anions ; Lithium ; Silanes ; Polysilyl dianions ; α,ω-Dilithiooligosilanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Me3Si)3Si(Me2Si)2(Me3Si)2SiLi (1) and LiSi(Me3Si)2(Me2Si)2Si(Me3Si)2Li (2) were synthesized by the reaction of (Me3Si)3Si(Me2Si)2Si(Me3Si)3 in THF with one or two mol-equivalents, respectively, of MeLi. Both 1 and 2 were characterized spectroscopically and by trapping reactions, and 1 also by X-ray crystallography.
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  • 10
    ISSN: 1434-193X
    Keywords: Fluorine ; Cycloadditions ; Nitrones ; Asymmetric induction ; Sulfoxides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3-(Fluoroalkyl)isoxazolidines 6 and -2,3-dihydroisoxazoles 8 have been obtained in enantiomerically pure form with good diastereoselectivity by 1,3-dipolar cycloaddition of diethyl fumarate and dimethylacetylene dicarboxylate, respectively, to the chiral fluorinated nitrone (R)-5. The latter has been prepared from the β-fluoromethyl-β-oxo sulfoxide (RS)-1, by a synthetic sequence where the chiral and enantiomerically pure sulfinyl function acts as a removable source of chirality. Reductive opening of isoxazolidines 6 then afforded amino fluoromethyl diols 7 in good yields.
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