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  • 1965-1969  (16)
  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 71 (1967), S. 2416-2424 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 72 (1968), S. 278-285 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 72 (1968), S. 1265-1271 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 23-35 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyacrylamide having a fluorescent residue at the chain end was prepared by polymerization of acrylamide in the presence of a fluorescent dye. The segmental motion of the chain end in dilute solution was studied by the fluorescence polarization method on the fluorescent polyacrylamide conjugates thus obtained. The linear relation between 1/p and T/η0 held for every sample studied in aqueous media, where p is the degree of polarization of the fluorescence, T is the absolute temperature, and η0 is the viscosity of the medium. The mean relaxation time 〈ρ〉 of the conjugate was evaluated from these data as a function of the molecular weight of the conjugate. The value of 〈ρ〉 increased slightly with molecular weight, varying from 3.3 × 10-9 to 7 × 10-9 sec. The absolute values of 〈ρ〉 and its molecular weight dependence suggest that 〈ρ〉 represents the mean rotational relaxation time for the cooperative motion of about ten monomeric units at the chain end. The effect of the mean extension of polymer chain on the segmental motion was found to be negligible.
    Additional Material: 7 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 37-45 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fluorescence polarization method has been used to study the micro-Brownian motion of a terminal segement of a polymer chain in concentrated solutions. A new apparatus for determining the fluorescence intensity and its polarization degree was designed. By using this apparatus, the rotational relaxation time 〈ρ〉 of the terminal segment of the fluorescent conjugates of polyacrylamide in aqueous polyacrylamide solutions was obtained as a function of polymer concentration from 0 to 65%, molecular weight of the conjugate from 3.5 × 104 to 3 × 105, and temperature from 10 to 30°C. The logarithm of 〈ρ〉 increased approximately linearly with increasing polymer concentration. This increase in 〈ρ〉, amounting to a factor of 20 times, was less marked than that in macroscopic viscosity. At concentrations less than 30%, 〈ρ〉 depended appreciably on the molecular weight of the conjugate.
    Additional Material: 8 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 85 (1965), S. 261-272 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die isothermen Viskositäten η von Polyäthylenoxidfraktionen und Mischungen dieser Fraktionen wurden im Bereich zwischen Monomerem (Glycol) und einem Molekulargewicht von etwa 105 bei einer Anzahl von Temperaturen zwischen 9 und 155°C (bei kleinem Geschwindigkeitsgefälle) gemessen.Die Art und Weise, wie η sich mit der Temperatur ändert, war vom Molekulargewicht unabhängig, wenn man von den niedrigsten Molekulargewichten absieht. Die Temperaturabhängigkeit folgt einer Beziehung vom WILLIAM-LANDEL-FERRY-Typ.Die Auftragung log η gegen log M̄v (M̄v ist das Viskositätsmittel des Molekulargewichts, das aus dem STAUDINGER-Index in Benzol bei 20°C bestimmt wurde) gab eine glatte Kurve mit scharfer Aufwärtskrümmung, die aber weder eine Asymptote mit einer Steigung von 3,4 im Bereich der hohen Molekulargewichte noch einen definierten Knick zeigte. Die Kurve hat beim höchsten Molekulargewicht eine Steigung von 5. Das vorliegende System gehorcht also nicht dem empirischen Viskositätsgesetz von FOX und LOSHAEK.PORTER und JOHNSON berichteten kürzlich über die gleiche Anomalie des Polyäthylenoxids. Ihre Messungen waren auf einen engeren Molekulargewichtsbereich beschränkt. Wo ein Vergleich möglich ist, stimmen sie mit unseren Werten befriedigend überein.
    Notes: Isothermal viscosities η (at low shear rates) of polyethylene oxide fractions and blends were measured in the range from the monomer (glycol) to a molecular weight of about 105 and at a number of temperatures between 9 and 155°C. The fashion in which η varied with temperature was independent of molecular weight, except in the region of low molecular weight, and fitted very well a relation of the WILLIAMS-LANDEL-FERRY type. Plots for log η vs. log M̄v (M̄v is the viscosity-average molecular weight estimated from the limiting viscosity number in benzene at 20°C.) gave a smooth curve of sharp upward curvature, showing no asymptote of slope 3.4 in the region of high molecular weight nor a definite break. The curve has a slope as high as about 5 at the highest molecular weight studied. Thus the present system does not obey the well-known empirical viscosity law of FOX and LOSHAEK. PORTER and JOHNSON had previously reported a similar anomaly of the molecular weight dependence of η of polyethylene oxide, although their data were limited to a narrower range of molecular weight than ours. In the region where comparison can be made, the two data agree quite satisfactorily with each other.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 90 (1966), S. 78-90 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die NEWTONschen Viskositäten η von 4 verschiedenen Polyäthylenoxid-Wasser-Systemen wurden im gesamten Konzentrationsbereich und bei verschiedenen Temperaturen zwischen 5 und 80°C gemessen. Die Molekulargewichte der Proben reichten von 62,07 (Glykol) bis 17500. Die Temperaturabhängigkeit von η variiert sowohl mit der Zusammensetzung der Lösung als auch mit dem Molekulargewicht. Die DOOLITTLE-Gleichung η = F(v2)exp[1/f(T,v2)] ist sehr genau erfüllt; dabei sind f das partielle freie Volumen, F der statistische Faktor und v2 der Volumenbruch des gelösten Polymeren. f als Funktion von v2 aufgetragen ergibt zur Abszisse konvexe Kurven; das entspricht den von OKADA et al. für Methacrylatpolymere in Diäthylphthalat gefundenen Verhältnissen. Die Division der experimentellen η-Werte durch exp[1/f(T,v2)] liefert F als Funktion von v2; diese ist innerhalb der Versuchsfehler von der Temperatur unabhängig. Die F-Werte der Oligomeren sind kaum merklich verschieden von dem Wert für reines Wasser, die der Polymeren dagegen sind viel größer.
    Notes: NEWTONian viscosities η of 4 poly(ethylene oxide)-water systems were measured over the complete range of composition and at a number of different temperatures between 5 and 80°C. The molecular weights of the samples used ranged from 62.07 (glycol) up to 17,500. The temperature dependence of η varied with both composition and molecular weight and fitted very well an equation of the DOOLITTLE type, η = F(v2) exp[1/f(T,v2)], where f is the fractional free volume, F the statistical factor, and v2 the volume fraction of the polymer solute. Values of f for each system evaluated as a function of T and v2 varied nonlinearly with v2 in all cases studied, giving curves convex downward. This behavior is similar to that found by OKADA et al. for methacrylate polymers in diethyl phthalate. Division of experimental values of η by exp[1/f(T,v2)] gives F as a function of v2, which was independent of temperature within experimental errors. The F's for the oligomers were not appreciably different from that for pure water, while the F's for the polymer fractions were much greater than that for pure water.
    Additional Material: 8 Ill.
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  • 8
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Light-scattering measurements were performed for a number of poly-γ-benzyl-L-glutamate (PBLG) samples in dimethylformamide (DMF) and in chloroform-formamide (C-F) at 25°C. Osmotic pressure data for some of these polypeptide samples in DMF at 37°C. were also determined. The scattering radii 〈S2〉1/2 in the two solvents were roughly proportional to the sample's weight-average molecular weight Mw. The lengths per monomeric residue h, calculated from the measured 〈S2〉1/2 and Mw with the assumption of a rigid rod of uniform density, were about 1.2 A. in DMF and about 1.5 A. in C-F. The measured values for the Mw/Mn ratio indicated that the samples used were quite polydisperse in molecular weight. If this effect is taken into account, the above values for h must be lowered drastically. In fact, application of Holtzer's procedure, which is capable of yielding h free of polydispersity effects, gave 0.85 A. for h in DMF and 1.16 A. for h in C-F. Since, according to the recent conclusion established by Parry and Elliott, the correct conformation of the PBLG molecule in helicogenic solvents must be the α-helix for which h is 1.5 A., these results imply that the overall shape of the PBLG helix cannot be a rigid rod, in contradiction to the earlier conclusion of Doty et al.
    Additional Material: 5 Ill.
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  • 9
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Simple approximate expressions have been derived from the theory of Zimm and Bragg for use in the analysis of experimental data on the helix-coil transition in polypeptide. On the basis of the resulting expressions practical procedures are proposed to determine two basic parameters characterizing a thermally induced transition, i.e., helix initiation parameter σ and enthalpy change for helix formation, ΔH. They have been applied to the data for poly(β-benzyl L-aspartate) (PBLA) with the result: σ = 1.6 × 10-4 and ΔH = -450 cal/mole for PBLA in m-cresol; σ = 0.6 × 10-4 and ΔH = 260 cal/mole for PBLA in chloroform containing 5.7 vol-% of dichloroacetic acid. This result gives evidence that σ may change not only from one polypeptide to another but also for a given polypeptide in different solvents. The change in limiting viscosity number [η] accompanying the transition was measured in the same solvents. The curve of [η] versus helical content had a relatively monotonic shape for the chloroformdichloroacetic acid solutions as compared with that for the m-cresol solutions, indicating that [η] depended largely on σ. Provided that [η] is a direct measure of the mean-square radius of gyration, 〈S2〉, the results are consistent with the theoretical predictions of Nagai and of Miller and Flory for 〈S2〉.
    Additional Material: 12 Ill.
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  • 10
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nine samples of poly-γ-benzyl-L-glutamate (PBLG), ranging in M̄w from 19,000 to 410,000, were examined viscomctrically and by ultracentrifugation with dimethylforma-mide (DMF) at 25°C. as helicogenic solvent. The data for [η] and s0 (limiting sedimentation coefficient) as functions of M̄w were fitted well by the theories for a rigid prolate ellipsoid of revolution whose major axis increases linearly with M̄w, but whose minor axis is independent of M̄w. This implies that the overall shape of the PBLG molecule in DMF is represented by a straight cylinder whose cross section is independent of its length. The length per monomeric residue h evaluated from [η] is about 1.3 A., whereas that from s0 is about 1.6 A. No adequate explanation for this difference in h can be found at present. More serious is the fact that these hydrodynamically evaluated values of h are appreciably larger than, the value obtained from our light-scattering measurements reported previously. All these values of h from our studies are not consistent with the value characteristic of the α-helix, for which h is 1.5 A. The concentration dependence of s0 was found to agree well with the recent theoretical prediction of Peterson for cylindrical macromolecules.
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