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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 5 (1967), S. 27-35 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The helix-coil transition temperature Tc of poly(γ-benzyl L-glutamate) in binary solvent mixtures of dichloroacetic acid and 1,4-dichlorobutane, 1-chlorooctane, or 1-chlorododecane have been measured. A treatment is presented with which the transition enthalpy can be calculated from the observed dependence of Tc on solvent composition. Results are compared with previously obtained calorimetric data. The underlying assumptions of the calculation are discussed.
    Additional Material: 2 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 4 (1966), S. 1015-1023 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of deuteration and of changes in solvent composition on the thermo dynamics of the helix-coil transition have been studied by calorimetric and optical measurements in the poly-γ-benzyl-L-glutamate-dichloroacetic acid-1,2-dichloro-ethanc system. For a given solvent composition, deuteration of the polypeptide and of the acid lowers the transition temperature Tc, while an increase in the volume fraction of acid in the solvent raises Tc. A rise in Tc is accompanied by a decrease in both the van't Hoff and the calorimetric heats of transition, but at different rates. The result is a temperature dependency in the Zimm-Bragg cooperation parameter σ. Possible causes of this result and its implications are discussed.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 15 (1969), S. 809-814 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental and analytical study was made to determine how well the material functions, derived from the Spriggs four-constant viscoelastic model, could describe the rheological properties of polymer melts. Viscosity and elasticity of selected polymer melts were experimentally determined in the rotational and oscillatory modes using a Weissenberg Rheogoniometer. The Spriggs model was chosen for study because of its success in describing experimental data for polymer solutions and because of its uniqueness in combining results from molecular theory with results from the theories associated with continuum mechanics. It was found that the model provides a good description of the rheological data for polymer melts and that some of the model parameters depend upon the molecular characteristics of the polymer. Since this model contains a small number of well defined constants, it should be useful in developing dimensionless engineering correlations for the complex flows encountered in processes of industrial importance. Deviations between the theoretical and experimental results are discussed and deficiencies of the model noted.
    Additional Material: 8 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 3 (1965), S. 241-247 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reversible helix-to-random coil conformational change which occurs in solvated poly-∊-carbobenzosy-L-lysine, a synthetic polypeptide, has been studied. The course of this cooperative transition, which in many ways resembles a first-order phase transition, was followed both by measuring changes in optical rotation as a function of temperature, and calorimetrically by determining the heat capacity of the solution through the transition region. From the latter measurements, the enthalpy of transition was calculated. From the results it has been shown directly, for the first time, that in a statistical thermodynamical sense, the transition in this system is significantly more cooperative than that undergone by poly-γ-benzyl-L-glutamate, a closely analogous polypeptide. Thus a previously held concept that the degree of cooperation might be quantitatively similar for a wide range of such systems has been shown, for at least one important example, not to be tenable.
    Additional Material: 3 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 9 (1970), S. 1429-1435 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enthalpy of denaturation of lysozyme was determined by measuring the heat, capacity of an aqueous solution of this protein in the vicinity of the transition temperature, 46 °C at pH 1. Within experimental error the calorimetric, heat (56 ± 8 kcal/mole) was found to agree with the van't Hoff transition enthalpy (63 ± 6 kcal/mole) determined from optical rotation measurements as a function of temperature. This indicates that denaturation of this protein can be interpreted in terms of a two-state model. Successive measurements of the same sample showed, from several lines of evidence, that the transition was about 80% reversible for the particular environmental conditions and thermal history involved in the study.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 27 (1989), S. 837-857 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An apparatus has been constructed that permits the measurement of time-dependent changes in pressure near the point of vitrification. The same instrument is used for measuring steady-state PVT properties, which are necessary for a proper analysis of the dynamic measurements. The former experiments are referred to as pressure-jump volume-relaxation (PJVR) measurements and serve as a direct probe of the structural relaxation process that occurs in all glasses. Experiments have been performed on polystyrene from 110 to 150°C and up to 2 kbar using pressure steps of 500 bars. The qualitative observations are analogous to those obtained at atmospheric pressure by rapid changes in temperature, namely (1) nonlinearity, (2) asymmetry, and (3) memory effects associated with complicated temperature or pressure histories. Each of these effects is accounted for semiquantitatively by a phenomenological order-parameter model that has been extended to include the effect of pressure. Deviations between theory and experiment increase as temperature and pressure increase, this being manifest mostly in a predicted recovery curve (expansion isobar) that recovers the equilibrium volume more quickly than the experimental data; the contraction isobars are in most cases predicted within experimental error. The adjustable parameters of the model are found to vary somewhat with pressure and temperature, apparently due to variations in δ and Δκ. The activation volume suggests that 10-20 monomer segments are involved in the recovery process, assuming that the activation volume itself represents only a fraction of the dynamic unit (as observed in molecular glasses).
    Additional Material: 14 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 637-655 
    ISSN: 0887-6266
    Keywords: organic-inorganic composites ; sol-gel ; TEOS ; TMOS ; SAXS ; morphology ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two morphological models have been proposed to describe small-angle x-ray scattering from organic-inorganic composite (OIC) materials. The first model invokes the idea of a liquid-like arrangement among noninterpenetrating fractal clusters, and the second employs an empirical correlation function that would be expected for a bicontinuous two-phase (B2P) picture with the inorganic portion exhibiting fractal characteristics. Simulated scattering profiles have been generated for direct comparison with experimental data. The samples studied were a triethoxysilane-endcapped bisphenol A epoxide resin (EAS) reacted in the presence of tetraethoxysilane (TEOS) under slightly basic conditions, and a random trimethoxysilane-functionalized copolymer of poly(methyl methacrylate) (MMA-TMS) with added tetramethoxysilane (TMOS), reacted in an acidic medium. Each morphology model qualitatively simulates the broad scattering maximum and limiting high-angle slope commonly seen in SAXS profiles. It is concluded that the inorganic phase in the EAS hybrid exhibits particle-like characteristics at length scales less than approximately 250 Å, and the organic and inorganic components are bicontinuous at larger distances. The MMATMS composite is better described by bicontinuous organic and inorganic phases with a periodic fluctuation of about 40 Å. The scattering maximum arises either from the mean separation of particles or a dominant wavelength in a concentration fluctuation, similar to that observed for spinodal decomposition. In either case, the SAXS peak position is related to the distance between junction points of the crosslinked organic polymer. © 1995 John Wiley & Sons, Inc.
    Additional Material: 16 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 26 (1988), S. 501-513 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The KAHR model of structural relaxation has been extended to include the effects of pressure upon the retardation times of glass-forming materials. The previously used methodology is applied with a continuous distribution of retardation times of the fractional exponential form. Several forms of the pressure dependence are examined. The combined temperature and pressure changes on structural recovery of glasses are addressed in this paper.
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 7 (1980), S. 35-40 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A pseudoracemic technique utilizing a stable isotope in one enantiomer was employed for the simultaneous determination of (R) and (S)-warfarin from plasma of human subjects. The assay includes high performance liquid chromatographic clean-up prior to mass spectral analysis to eliminate ion interferences from either co-administered drugs or contamination of the source. The assay is reliable, accurate and precise to within 5% at the submicrogram level.
    Additional Material: 3 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 21 (1981), S. 1181-1187 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 conformational and enthalpic changes that occur in poly(vinyl chloride) (PVC) glasses that have been vitrified from the melt under pressure have been examined by Fourier transform infrared spectroscopy and quantitative differential scanning calorimetry. It is shown that these pressures freeze in the high energy states that are characteristic of the vitrification temperature and increase the apparent glass transition temperature of the polymer. In addition, pressures in excess of the vitrification pressure, cause intermolecular effects that can be relaxed out below Tg. Both of these processes create characteristic endothermic and exothermic changes in the apparent heat capacity of the glass that appear over a period of time and are sensitive functions of the glass formation processes as well as the subsequent annealing history. The endothermic events are interpreted as the stress perturbed volumetric relaxation process white the exotherms are associated withh the release of the frozen in stresses.
    Additional Material: 11 Ill.
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