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  • Articles  (16)
  • General Chemistry  (9)
  • Polymer and Materials Science  (5)
  • Encapsulation  (2)
  • 1995-1999  (16)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Molecular genetics and genomics 250 (1996), S. 734-741 
    ISSN: 1617-4623
    Keywords: Key words Bacillus thuringiensis ; cry gene expression ; Encapsulation ; Sigma factors ; Sporulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The sigE and sigK genes, encoding the sporulation-specific sigma factors σ35 and σ28 of Bacillus thuringiensis, were each disrupted by inserting a gene conferring resistance to kanamycin into their coding sequence. The B. thuringiensis SigE- and SigK- mutant strains were blocked at different sporulation stages and were unable to sporulate. The SigE- strain was blocked at stage II of sporulation, whereas the SigK- strain was blocked at stage IV. The expression of a cryIAa′-′lacZ transcriptional fusion was analysed in these genetic backgrounds and it was found that both sigma factors are involved in the in vivo transcription of this gene. However, the SigK- strain harbouring the cryIAa gene produced amounts of toxin similar to those produced by the B. thuringiensis Spo+ strain. The toxins accumulated in the mother cell compartment to form a crystal inclusion which remained encapsulated within the cell wall. Thus, transcription from the σE-dependent promoter alone (Bt I promoter) is sufficient to support high levels of toxin production in B. thuringiensis.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Molecular genetics and genomics 250 (1996), S. 734-741 
    ISSN: 1617-4623
    Keywords: Bacillus thuringiensis ; cry gene expression ; Encapsulation ; Sigma factors ; Sporulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract ThesigE andsigK genes, encoding the sporulation-specific sigma factorsσ 35 andσ 28 ofBacillus thuringiensis, were each disrupted by inserting a gene conferring resistance to kanamycin into their coding sequence. TheB. thuringiensis SigE− and SigK− mutant strains were blocked at different sporulation stages and were unable to sporulate. The SigE− strain was blocked at stage II of sporulation, whereas the SigK− strain was blocked at stage IV. The expression of acryIAa′-′lacZ transcriptional fusion was analysed in these genetic backgrounds and it was found that both sigma factors are involved in the in vivo transcription of this gene. However, the SigK− strain harbouring thecryIAa gene produced amounts of toxin similar to those produced by theB. thuringiensis Spo+ strain. The toxins accumulated in the mother cell compartment to form a crystal inclusion which remained encapsulated within the cell wall. Thus, transcription from theσ E-dependent promoter alone (Bt I promoter) is sufficient to support high levels of toxin production inB. thuringiensis.
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  • 3
    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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  • 4
    ISSN: 1434-193X
    Keywords: Catenanes ; Mechanically interlocked molecules ; Molecular recognition ; Rotaxanes ; Template-directed synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -A [2]catenane, able to bind π-electron-rich guests inside the cavity of one of its two macrocyclic components has been designed and synthesized using supramolecular assistance. This recognition motif has been exploited to template the formation of a so-called rotacatenane - i.e., a molecule composed of a dumbbell-shaped component threaded through the cavity of one of the two mechanically interlocked macrocyclic components of a [2]catenane. The structure of this [2]catenane, as well as that of a model [2]catenane, have been characterized unequivocally by single-crystal X-ray analyses. Furthermore, some of the co-conformational changes associated with these mechanically interlocked molecules in solution have been probed by variable-temperature 1H-NMR spectroscopy.
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  • 5
    ISSN: 1434-193X
    Keywords: Co-conformation ; Molecular recognition ; Planar chirality ; Rotaxanes ; Template-directed synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The template-directed syntheses of three [2]rotaxanes possessing either chiral centers or elements of planar chirality, in one of their two mechanically interlocked components, have been realized and their solid-state structures have been analyzed by X-ray crystallography. In one instance, an enantiomerically pure dumbbell-shaped component incorporating a 1,5-dioxynaphthalene recognition site and two (1R,2S,5R)-menthyl stoppers was employed to template the formation of the achiral tetracationic cyclophane, cyclobis(paraquat-p-phenylene). The resulting enantiomerically pure [2]rotaxane was isolated in a yield of 55%. In the other two instances, an achiral 1,5-dioxynaphthalene-based dumbbell-shaped component was employed to template the formation of bipyridinium-based cyclophanes possessing either one or two elements of planar chirality. The resulting [2]rotaxane, possessing one element of planar chirality, was isolated as a racemate in a yield of 24%. The related [2]rotaxane, possessing two elements of planar chirality, was isolated as a mixture of a meso form and an enantiomeric pair in an overall yield of 28%. The 1H-NMR-spectroscopic analysis of this mixture revealed a diastereoisomeric ratio of 4:1. A degenerate co-conformational change was identified by variable-temperature 1H-NMR spectroscopy in all [2]rotaxanes. The symmetry loss arising from the introduction of one or two elements of planar chirality enabled the elucidation of the mechanism of this dynamic process in two instances.
    Additional Material: 12 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 198 (1997), S. 3863-3869 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two poly(2-vinylpyridine)s fully quaternized with a ω-(4′-methoxy-4-biphenylyloxy)-alkyl group (alkyl chain of 9 and 11 carbon atoms) have been synthesized by the well known spontaneous polymerization of vinylpyridinium salts. When heated, these polymers (P2VPC9 and P2VPC11) show thermotropic liquid crystal properties. According to the X-ray diffraction data, the observed smectic mesophase in both polymers is of the type A (SA). Results are discussed in comparison with other molecular and polymeric pyridinium salts previously described. A molecular arrangement model for the P2VP derivatives is proposed.
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  • 7
    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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  • 8
    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.
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 197 (1996), S. 1349-1360 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Model compounds for a series of polyesters in which 3,6,9, and 12-rotatable CH2—O and CH2—CH2 bonds separate rigid units have been studied using the efficiency of nonradiative singlet energy transfer from naphthalene to anthracene. The model compounds have the structure naph-CO—(OCH2CH2)m—OOC-anth with m of 1-4, where naph and anth denote 2-naphthyl and 9-anthranyl groups, respectively. This series of compounds covers a larger range of potential separation of the two chromophores than was possible in an earlier study, in which the flexible spacers consisted of 2-6 methylene units. The nonradiative singlet energy transfer has an efficiency that depends on the solvent viscosity and on m. The theoretical analysis employs a rotational isomeric state model for the conformations of these molecules. The Förster radius for transfer from naphthalene to anthracene in this system is 16 ± 2 Å, and is nearly independent of whether the spacers are constructed from oxyethylene or methylene units.
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  • 10
    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.
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