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  • 1
    Electronic Resource
    Electronic Resource
    Photooxygenation of 3,3-dialkylsubstituted allyl alcohols. Occurrence of syn preference in the ene addition of 1O2 at E/Z-isomeric allyl alcohols (1979)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 816-829 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dye-sensitized photooxygenation (1O2-reaction) of the symmetrically 3,3-dialkyl-substituted allyl alcohols 1-6 (A, Table 1) and the E- and Z-isomers of the 3-methyl-3-alkylsubstituted allyl alcohols 7-11 (A1, Table 2) has been studied. The α, β-epoxyaldehydes B and B1 and the β-hydroperoxy-homoallyl alcohols C, C1 and D1 were practically the sole oxygenation products formed. The rate and selectivity of the 1O2 additions were found to be markedly dependent on the degree of substitution (i.e. H-availability) at the allyl position which is Z-orientated to the carbinol group. The allyl alcohols with a Z-3-methyl group, 1 and the E-isomers of 7 to 10, showed practically the same reactivity towards 1O2 and formed only the two oxygenation products of type B1 and C1 (ratio close to 60:40). In contrast, the allyl alcohols with a Z-3-methylene group, 2 and the Z-isomers of 7 to 9, reacted more slowly with 1O2 and yielded all the three possible products B1, C1 and D1 in a very different ratio of ∼ 80:10:10. However, from both the E- and Z-isomers of the alcohols 7 to 10 the formations of the two oxygenation products were always strongly favoured (85-100%) which result from 1O2 additions at the disubstituted side of the double bond. This behaviour is thus completely analogous to that of the corresponding trisubstituted olefins previously studied [1]The same side-specific selectivity in 1O2 ene additions to several E/Z-isomeric and deuterium-labelled olefins has also been described recently by C.M. Stephenson et al. [2] (we thank Dr. V. Rautenstrauch and Prof. C.W. Jefford for informing us about this work). The similar behaviour of enol ethers, which react with 1O2 preferentially at the RO-substituted side, had been observed earlier by C.S. Foote et al. [3] and extended to numerous derivatives by J.M. Conia et al. [4] [5]. and follows a new selection rule, termed syn-preference [1], in the ene addition of 1O2.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19790620318
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  • 2
    Electronic Resource
    Electronic Resource
    Asymmetric Synthesis of Diazepino-β-lactams by [2 + 2] Cycloaddition of an ‘Evans-Sjogven’ Ketene with 1H-1,2-Diazepines (1991)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 74 (1991), S. 767-773 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ketene derivative of the chiral oxazolidinone 1 underwent non-concerted stereo specific [2 + 2] cycloadditions with the (Z)-imine moiety of diazepines 2, leading thereby with good diastereoselection to the trans-β-lactam adducts 3 (major) and 4 (minor). The absolute configuration of the major cycloadduct 3a was determined by an X-ray analysis. Its formation is discussed in terms of minimisation of steric interaction in the two transition states which give sequencially the zwitterionic intermediates and the final cycloadducts.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19910740410
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  • 3
    Electronic Resource
    Electronic Resource
    Mini-chiuz (1991)
    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 25 (1991), S. 8-26 
    Details
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ciuz.19910250103
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  • 4
    Electronic Resource
    Electronic Resource
    Stereoselective binding of etodolac to human serum albuminPresented at the Second International Symposium on Chiral Discrimination, May 27-31, 1991, Rome, Italy. (1992)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 4 (1992), S. 240-246 
    Details
    ISSN: 0899-0042
    Keywords: NSAID ; chirality ; enantiomers ; protein binding ; equilibrium dialysis ; fluorescent specific markers ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The protein binding of etodolac enantiomers was studied in vitro by equilibrium dialysis in human serum albumin (HSA) of various concentrations varying from 1 to 40 g/liter, by addition of each enantiomer at increasing concentrations. In the 1 g/liter solution, at the lowest drug levels, the (R)-form is more bound than its antipode, the contrary being observed at the highest drug levels. For higher albumin concentrations, S was bound in a larger extent than R. Using the displacement of specific markers of HSA sites I and II, studied by spectrofluorimetry, it was suggested that R and S are both bound to site I, while only S is strongly bound to site II. © 1992 Wiley-Liss, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530040407
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  • 5
    Electronic Resource
    Electronic Resource
    Hydrophobicity and stability for a family of model proteins (1993)
    New York : Wiley-Blackwell
    Biopolymers 33 (1993), S. 1185-1193 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: According to the conventional definition, the hydrophobic effect is a result of thermodynamic changes occurring when a nonpolar group dissolves in water and attributable to the fact that water in contact with such a group has special structural and energetic properties. Disagreement now exists as to whether this effect promotes or hinders protein denaturation. Taking the heat capacity change of unfolding as a measure of the hydrophobicity of the protein interior, others have shown that protein stabilities are systematically affected by changes in hydrophobicity. It has been suggested that the observed trends show that hydrophobic hydration is intrinsically a destabilizing factor. Model calculations using known equations for the stability curves and certain simplifying assumptions now show that such regularities provide no evidence for or against this conclusion. All available data can be rationalized if hydrophobic terms are evaluated from models that require a positive hydrophobic contribution to the Gibbs energy of unfolding. The calculations also confirm the recent finding that any set of proteins with denaturation temperatures between about 330 and 380 K that exhibits entropy convergence at about 386 K is thermodynamically required to show enthalpy convergence at approximately the same temperature. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360330805
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  • 6
    Electronic Resource
    Electronic Resource
    Viscoelastic properties of styrene-co-methyl methacrylate random copolymers (1991)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 29 (1991), S. 933-943 
    Details
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viscoelastic properties of styrene-co-methyl methacrylate random copolymers have been determined over a temperature range covering the glass transition, the rubbery plateau, and the terminal zone and compared with polystyrene and polymethyl methacrylate homopolymers. Nonlinear behavior was observed in the variations of most of the physical and rheological characteristics with the methyl methacrylate content in the copolymer. Results are interpreted in terms of the rupture of polar-polar intermolecular interactions between ester groups due to the presence of styrene units.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/polb.1991.090290804
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  • 7
    Electronic Resource
    Electronic Resource
    Study of the carbon fiber-Poly(Ether-Ether-Ketone) (PEEK) interfaces, 3: influence and properties of interphases (1991)
    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 2 (1991), S. 161-169 
    Details
    ISSN: 1042-7147
    Keywords: Crystalline interphase ; Interfacial polymer chain orientation ; Elastic modulus of interphase ; Stress-free temperature ; Reversible energy of adhesion ; 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
    Notes: The aim of this third part is to analyze the structure and properties of the interfacial region between carbon fibers and PEEK as a function of different thermal conditioning treatments. First, it is shown by means of optical microscopy that the interfacial zone is not different from the bulk matrix when standard cooling conditions are used. On the contrary, a transcrystalline interphase is formed near the carbon fiber surface in systems that have been subjected to isothermal treatments. By comparison with previous results concerning the mechanical properties of the fiber-matrix interface, it appears that the interfacial shear strength decreases in the presence of a transcrystalline interphase or when the crystallization rate of PEEK increases. Moreover, it seems that the “constraint state” of the amorphous phase of PEEK near the fiber surface could also play a role in the interfacial shear strength. Secondly, a method is proposed in order to estimate the elastic modulus of crystalline interphases. It seems that this modulus is strongly dependent on the crystallization rate of the polymer. Finally, the determination of the stress-free temperature, defined as the temperature at which a longitudinal compressive stress just appears on the carbon fiber during the processing of the composites, is performed by recording the acoustic events corresponding to the fragmentation process in single-fiber composites. The results confirm that the crystallization rate and the “constraint state” of the amorphous phase of the matrix play an important role in the mechanical behavior of carbon fiber-PEEK interfaces.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pat.1991.220020401
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  • 8
    Electronic Resource
    Electronic Resource
    Phosphonic systems. Part 15. Addition of diethyl prop-2-enylphosphonate to aldehydes: Fragmentation vs. isomerization of kinetic productsDedicated to Prof. Adrian Gibbs Brook on the occasion of his seventieth birthday.Part 14 of this series: J. P. Gerber, T. A. Modro, Phosphorus, Sulfur and Silicon, in press. (1994)
    New York, NY [u.a.] : Wiley-Blackwell
    Heteroatom Chemistry 5 (1994), S. 287-291 
    Details
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lithiated diethyl prop-2-enylphosphonate adds to an aliphatic or an aromatic aldehyde, yielding a diastereomeric mixture of the kinetically controlled α-adduct. Upon warming, these adducts decompose back to starting materials to give finally the thermodynamically controlled γ-adducts, or undergo fragmentation to diethyl phosphate and (E) dienes. The distribution of the first product between these two pathways is a function of the aldehyde (aromatic vs. aliphatic) and of steric interactions operating within the two diastereomers of the adduct.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hc.520050314
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  • 9
    Electronic Resource
    Electronic Resource
    Electrospray mass spectrometry on a magnetic sector instrument applied to heteropolyacids (1994)
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 8 (1994), S. 692-694 
    Details
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Electrospray mass spectrometry has been applied to ionic inorganic systems such as heteropolyacids in methanol + water (1/1) or acetonitrile + water (1/1) solutions. Negative-ion mass spectra were obtained on four different heteropolyacids. Heteropolymolybdates H3PMo12O40 and H4PMo11VO40 and heteropolytungstates H3PW12O40 and H4SiW12O40 gave ions with different charges. H3PMo12O40 gave ions of m/z 1822, 912 and 608 which correspond respectively to [PMo12O403- + 2H+], [PMo12O403- + H+]2- and [PMo12O40]3- ions. Resolution of 1:2200 has demonstrated the charge of each ion acquired. Furthermore, the isotope distribution of the observed ions was in good agreement with theory. Thus, electrospray mass spectrometry has become a powerful soft ionization technique for the analysis of such ionic compounds, provided they are soluble and stable in the solvent system used.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/rcm.1290080905
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  • 10
    Electronic Resource
    Electronic Resource
    Fractional turbidimetric analysis of the molar substitution of hydroxyethyl cellulose (1966)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 10 (1966), S. 1285-1294 
    Details
    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: High quality packaging films from hydroxyethyl cellulose of low degree of substitution (DS) are being produced commercially in this country and abroad. Increasing demand for this and a variety of other applications requires a rapid and simple production control method for determining hydroxyethyl substitution of cellulose. None of the known analytical methods fulfills these requirements. The present paper describes a method which is based on the relationship between the solubility and the molar hydroxyethyl substitution of hydroxyethyl cellulose. A washed and dried sample of hydroxyethyl cellulose is dissolved in 7% aqueous sodium hydroxide. Methyl alcohol, a nonsolvent, is used to precipitate a fraction of the sample. The turbidity of the equilibrium system is determined and optical density readings are related to molar substitution. The method is most useful in low DS ranges of 2-8% EtO but is susceptile to broader application through adjustment of the composition of the solvent-nonsolvent mixture. Relatively large variations in DP can be tolerated. The molar substitution level of an hydroxyethyl cellulose sample can be obtained in 40 min. by this method, making it a practical production control technique.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1966.070100906
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