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  • 1965-1969  (8,218)
  • 1920-1924
  • 1840-1849
  • Polymer and Materials Science  (8,218)
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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 8 (1969) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 8 (1969), S. 21-27 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An increase in temperature causes an increase in the amplitudes of intramolecular and intermolecular motions and mainfests itself as an increase in the effective radii of the various atoms, especially hydrogen atoms. If one uses a Lennard-Jones 6-12 potential function to account for nonbonded interactions, this increase in the radius of the hydrogen atom is equivalent to a modification of the coefficient of the repulsive part of the Lennard-Jones potential. Accordingly, this effect of increasing temperature on the helix sense of several polyamino acids is computed by allowing the effective radius of the hydrogen atom to increase. It is found that the preferred sense of several polyamino acid helices changes from right- to left-handed as the temperature is increased. This accounts for recent experimental observations of changes in helix sense with temperature.
    Additional Material: 2 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 8 (1969), S. 57-68 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potentiometric titrations and some complementary optical rotation data are presented for solutions of poly(L- glutamic acid) (PGA) in several H2O-ethanol mixtures. The data allow the determination of the intrinsic pK (pK0), slope of the apparent. pK (pKapp), versus degree of ionization curves and of the enthalpy of ionization as a function of ethanol concentration. The variation of the degree of ionization at which the helix-coil transformation occurs with ethanol and temperature is also determined. Finally free energy, enthalpy, and intropy changes associated with the helix-coil transformation for the uncharged conformers are determined from the titration curves. The effect of the ethanol is to increase the stability of the helical conformation of PGA for both the charged and the uncharged forms of the polymer. The stabilization of the uncharged helix is essentially an entropic effect.
    Additional Material: 8 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 8 (1969), S. 91-99 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Infrared spectra of polypeptides were measured in the region of 1800-400 cm-1. For the α-helical form, disordered form, and antiparallel-chain β-form, amide V band- arising from N-H out-of-plane bending models were observed at 610-620, around 650, and 700-705 cm-1, respectively, and amide V′ bands arising from N-D out-of-plane bending modes were observed at 455-465, around 510, and a 515-530 cm-1, respectively. These correlations are useful for conformation diagnoses, particularly for copolyamino-acids or proteins which are not oriented. The nature of low-frequency amide bands are discussed with reference to potential energy distributions calculated for the α-helical form and β form.
    Additional Material: 6 Ill.
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  • 5
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some experimental data are given on the infrared spectra between 3300 and 3500 cm-1 of dilute solutions in carbon tetrachloride of three types of model compounds: CH3-CONH-CH(R1)-CONH(R2), (I); CH3-CON(CH3)-CH(R1)-CONH(R2), (II) and CH3-CONH-CH(R1)-CON(R2)2, (III). In studying the N-H stretching bands, it was found that there are two types of intramolecular hydrogen bonds in these molecules; these result in two different cyclized conformations, C5 and C7, which contain respectively, five and seven atoms in the ring. By using model substances I, II, and III, in which the nitrogen atoms are unequally substituted, it is possible to identify the N-H stretching bands which are to be ascribed to the N-H oscillators included in the two different chelated conformations. It is found also that the stretching frequency of a free N-H oscillator depends upon the substituent on the nitrogen atom. Thus, it is possible to observe, with some of the model compounds I, four different absorption bands located at 3340, 3420, 3440, and 3460 cm-1. The first two are ascribed to the N-H oscillators included in the H—bonds which lock the C7 and C5 conformations; the last two correspond to free N-H which differ with the substituent on the nitrogen atom.
    Additional Material: 10 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 8 (1969), S. 153-155 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 207-213 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular orbital calculations of the extended Hückel type have been used to study the conformations of glycyl and alanyl residues in ground and excited states. The ground-state surfaces show features similar to those obtained with the standard calculational methods in which the total energy is partitioned into components such as torsions, nonbonded and electrostatic interactions. The molecular orbital calculations provide the first independent theoretical check on such calculations. The excited-state surfaces, Uniquely available from the molecular orbital calculations, exhibit a better definition and sharpening of potential minima in the sterically allowed regions.
    Additional Material: 4 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: We derive equations for calculating the number-, weight-, and z-average lengths between single-strand breaks in DNA molecules. Provision is made for the existence of preformed breaks under genetic control: these are assumed to be fixed in number in each molecule, but may be variable in position. Breaks due to random degradation may be superimposed on the pre-existing breaks. An example is given for illustrative purposes.
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 223-239 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformation in solution of fractionated 30 S and 19 S ribosomal RNA from rabbit reticulocytes has been studied by optical rotatory dispersion, analysis of thermal melting profiles and their derivatives, and spectrophotometric acid-base titration. From a consideration of the limitations of these methods, it has been possible to set limiting values on the degree of base-pairing and the lengths of the double helices: between 60 and 80% of the bases in 19 S and 30 S RNA are estimated to be paired. The paired segments are not shorter than 4 base pairs, and evidence from other sources is available which indicates that they are not longer than 8-16 base pairs. The spread of helix lengths is greater in the 30 S than in 19 S RNA; and other differences are noted. Several distinct populations of double helices, differing in their thermal stability, are present. Estimates are presented from spectrophotometric and titration data for the base compositions of the paired and unpaired regions.
    Additional Material: 9 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 251-263 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A small perturbation analysis is carried out to determine the stability of a fluid containing two layers of diffusing solutes in a common solvent and acted upon by a uniform gravitational field. It is found that instability can arise even though the unperturbed diffusion does not lead to the formation of a density inversion within the fluid.
    Additional Material: 5 Ill.
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  • 11
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 475-493 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of denaturation of DNA have been studied by relaxation techniques. Examination of the terminal relaxation times for a variety of DNA's under a variety of conditions has shown that DNA denaturation is principally a hydrodynamically limited process. Measurements within the helix-coil transition have demonstrated that the experimentally measured terminal relaxation times are a function of the following: (1) position in the helix-coil transition; (2) ionic strength of the solvent; (3) solvent viscosity; (4) DNA concentration; (5) molecular weight; (6) number and position of single-strand breaks. The dependence of the terminal relaxation time on the above mentioned factors can be attributed to hydrodynamic effects. Thus a hydrodynamic model for DNA unwinding is required. The model which best fits the data involves the assumption of a rotational frictional coefficient independent of molecular weight. This assumption is suggested by the fact that the relaxation time is proportional to the first power of the molecular weight.
    Additional Material: 9 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 495-502 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sodium counterion association with partially neutralized poly(D-glutamic acid) or poly(DL-glutamic acid) was measured by use of Wall's transference method with radioactive sodium. In the region where both polyacids are in completely random coil form, fractions of association were considerably less than that with poly(acrylic acid) in the same region of degree of neutralization. Even in the region where poly (D-glutamic acid) is in the helical form, the fraction of association was less than that with poly(acrylic acid) in the same region. No pronounced characteristics attributable to counterion association corresponding to the helix-coil transition could be found. The association phenomena were discussed on the basis of a rodlike model of polyelectrolyte.
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  • 14
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 411-415 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The isomerization of poly-L-proline in different solvents has been studied by NMR spectroscopy. Different resonance signals for the CHα protons have been obtained for the two different helical conformations of thus compound, namely form I and form II.
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  • 15
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 417-422 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-β-N-diphenylmethyl-L-asparagine and poly-γ-N-diphenylmethyl-L-glutamine were prepared from the corresponding N-carboxyanhydrides. Poly-L-aspuragine and poly-L-glutamine were obtained by removal of the diphenylmethyl protecting groups with liquid anhydrous hydrofluoric acid.
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  • 16
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 379-393 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Hydrogen-tritium exchange character of poly-D,L-alanine was studied in detail as a model for the hydrogen exchange behavior of the unhindered, polymeric peptide group. The random chain nature of poly-D,L-alanine was evident in the uniformity of exchange rate of all its hydrogens and in the similarity between this rate and that of random chain poly-D,L-lysine and other known, unhindered secondary amide groups. An equilibrium isotope effect favoring the binding of tritium over protium to the extent of 21% was measured. Specific acid and base catalysis of the exchange and the absence of detectable general catalysis were demonstrated. Apparent energy of activation is 17 kcal/mole for deprotonation, largely due to dependence of Kw on temperature, and 15 kcal/mole for protonation, which correlates with the extreme apparent pK. The hydrogen -tritium exchange half-time rate; of poly-D,L-alamine at any pH and temperature (T: °C) is given by the equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ \[t_{\frac{1}{2}} \,(\min )\, = \,200\,\, \times \,10^{0.05{\rm T}} /\,[10^{{\rm pH} - 3} \, + \,10^{3 - {\rm pH}} ]\] $$\end{document}
    Additional Material: 9 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 581-593 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The specific rotation of starch components, corrected for refractive index variation, exhibits a discontinuity in the region of the water-dimethyl sulfoxide (H2O-DMSO) system that corresponds to the composition of the complex 2H2O-DMSO. This discontinuity is a property dependent upon the presence of a number of consecutively linked α-1,4 glucose units and, therefore, must reflect a change in symmetry of a segment, of polymer chain. The optical rotation of amylose between 26.5 and 92.5°C. does not change in DMSO and is only slightly lowered in water at the higher temperature. The behavior of amylose in both DMSO and H2O is like that of a random coil, as indicated by viscosity and sedimentation measurements. These results may be interpreted either as being compatible with models of amylose in solution in which the polymer backbone has helical twist, or as indicating removal of strong interactions between polymer chain segments by a good solvent.
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  • 18
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 614-618 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 21
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 1-3 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 22
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 5-19 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The osmotic pressure equation for nonideal, associating systems of the type nA +mB ⇄ AnBm, has been derived, by using the assumption yAnBm/yAnyBm = 1. This treatment can also be applied to related associations such as nA + mB ⇄ AB + AB2 + A2B + …. From osmotic pressure experiments on the pure reactants it is possible to obtain the molecular weights (MA and MB) of the reactants and also the virial coefficients (BAA and BBB) of the reactants. The osmotic pressure of a nonreacting mixture of A and B can be calculated from these measurements. It can be used along with osmotic pressure measurements on equilibrium mixtures of A and B to obtain expressions containing the equilibrium constant (or constants) and the cross-virial coefficients (BAB and BBA). Several procedures are described for the evaluation of the equilibrium constant (or constants) and the BAB or BBA terms. It appears that this procedure is a general one which is applicable to associations of the type nA + mB ⇄ AB + A2B + AB2 + …. By correcting for nonideal behavior, one should then be able to apply it to any method available for analyzing ideal associations of the types considered here. In addition it is possible, subject to certain restrictions, to analyze associations of the type 3A + B ⇄ A2 + AB.
    Additional Material: 3 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 39-58 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method has been developed for characterizing at, submicrogram levels the heterogeneity of histones from purified nuclei. The histones are eluted with a smooth concentration gradient from nuclei trapped in polyacrylamide-gel threads and are collected in a micro fraction collector suitable for volumes in the 10-100 μl range. The gradient and fraction collection systems are governed by cam driven syringes. Samples obtained are subjected to electrophoresis in a starch-gel system and the gels are stained with a highly sensitive stain specific for guanidinium groups. Seven major and a similar number of minor components are demonstrated in the histones. The method of differential elution of trapped macromolecules is suitable for use with systems other than nuclei and histones.
    Additional Material: 9 Ill.
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  • 24
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is presented for the treatment of distribution functions obtained by ultra-centrifugal sedimentation velocity experiments on the plasma lipoproteins, so that adequate corrections can he made for the effects of diffusion and concentration dependence of the sedimentation coefficient. The method involves the use of modified equations derived from those presented in 1952 by Gosting for the transform from g* (S) to g(S) distributions. The evaluation of the molecular parameters of lipoprotein density and size, from a set of g(Si°) distribution functions obtained in solvents of varying density, is also outlined. Preparations of the β-lipoprotein of human plasma are found to follow a bivariate normal distribution that requires evaluation of five parameters, x̄1, σ1, x̄2, σ2and p. The first two represent the mean and standard deviation of the lipoprotein density, the third and fourth the same quantities for the size, expressed as ft “logarithmic diameter parameter”, and the final value is a measure of the correlation between these two variables.
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  • 25
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 133-133 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 26
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 27
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 155-171 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-resolution nuclear magnetic resonance spectra at 100 MHz and 220 MHz have been obtained on two samples of poly-L-alanine of differing molecular weights (2500 and 42 500) in the chloroform-trifluoroacetic acid system under various conditions of solvent composition, temperature, and polypeptide concentration. Separate helix and random coil peaks are observed for the α-CH and peptide NH backbone proton resonances, thereby permitting the determination of helix content. This observation of separate peaks demonstrates that the lifetimes of the helix and random coil portions of poly-L-alanine have lower limits of about 10-1 sec. It is suggested that solvent-peptide versus peptide-peptide hydrogen bond competition, coupled with a destabilizing effect of the trifluoroacetic acid on the helix, is responsible for the helix-random coil transformation.
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  • 28
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 135-153 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The combination of an agarose gel (Bio-Gel A) and a dioxane-water (1:1) solvent system allowed the fractionation, on a preparative scale, of a very polydisperse, non-derivatized lignin preparation (enzymatically liberated lignin prepared from sweetgum sapwood with Lenzites trabea). Three fractions differing markedly in molecular weight were obtained. A gel of crosslinked alkylated dextran (Sephadex LH-20) with the same solvent system allowed division of the lowest molecular weight fraction into two fractions. These materials were characterized by measurements of intrinsic viscosity and number-average molecular weights in dimethylformamide and dioxane-water. It was established that the two highest molecular weight fractions were associated in an average trimeric form in dioxane-water (1:1) as compared to the form (considered to be molecular) that occurred in dimethylformamide. Molecular size distributions and eluant volumes of the fractions were determined with a Sephadex G-100-formamide system, the latter being one of the most powerful nonaqueous solvents for lignin. Adsorption effects were known to be absent in this case, and the lignin molecules were considered to be unassociated in formamide. The four fractions were distinguishable with the formamide-G-100 system, thus indicating that the original fractionation was based on molecular size. The enzymatically liberated lignin contained molecules that comprised a continuum of molecular weights from approximately monomeric to molecules that were at the limit of the solvating power of dioxane-water (1:1) and dimethylformamide. Limited physicochemical data were consistent with a compact, approximately spherically symmetric shape of the lignin in solution.
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  • 29
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 189-197 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A comparison has been made of the intrachain potential energy of an infinite straight α-helix of poly-L-alanine with that of the distorted form adopted in a coiled coil conformation. The energy terms included were the van der Waal's, electrostatic, hydrogen-bond, and the rotational potential terms. The results indicate that the potential energies of the structures investigated are almost the same, and so a transformation from one state to another may occur without significant changes in potential energy. Particular care has been taken to ensure that the electrostatic and van der Waal's interaction terms are fully convergent. The values obtained for the α-helix were compared with those already published, and some significant differences were found.
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  • 30
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ultraviolet optical rotatory dispersion curves of mucopolysaccharides exhibit particular Cotton effects in the spectral region of the n-π and π-π amide transitions. Two general patterns emerge: (1) enhancement of negative rotation and of the first negative Cotton effect (troughs 217-220 mμ) and (2) relative dominance of the positive Cotton effect in the π-π transition region (peak ∼198 mμ). Groups (1) and (2) can be correlated with a structural difference in the linkages of the amino sugars: (1) occurs with polymers containing 3-1-linked glycosamino sugars and (2) with glycosamino moieties linked 4-1 by either α- or β-glycosidie bonds. Measurements of the circular dichroic absorption bands support the qualitative conclusions from optical rotation. All mucopolysaccharides exhibit a first, negative band centered at 208-211 mμ, while only those in group (2) show, in addition, a positive band centered at 189-192 mμ. A suggested unifying model considers that difference in kind and/or degree of preferred geometry of the amide groups obtains from two forms of secondary order: (1) having a linear hydrogen bond from the N (acceptor) to the (C2)O - H of the preceding uronic acid and (2) having a linear hydrogen bond from the N (acceptor) to the (C2 or 3) O - H of the following sugar. The hydrogen bonds would have similar strength but opposite directions in two systems towards the nonreducing end (1) or towards the reducing end (2)], closing eight-membered rings
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  • 31
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 99-106 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The myosin molecule was extracted from the smooth muscle parts of horse esophagus and purified by ammonium sulfate fractionation. The schlieren pattern of the sedimentation velocity run showed a very sharp single peak of.5.9. S (s20,w). Molecular weight of the protein was measured by means of the Archibald and sedimentation equilibrium methods, both in 0.5M KCI buffered by 1/150 M phosphate at pH 7.5 and at 5°C. The values obtained were 6.25 × 105 and 5.81 × 105respectively, for the two methods. The second virial coefficients were 1.1 × 104 and 1.2 × 10-4 ml/g. Denatured smooth muscle myosin was prepared in a solution of 5M guanidine HC1 containing 0.4 M KC1 and 0.2 M β-mercaptoet hanol buffered at pH 8.0. The weight-average molecular weight of the denatured smooth muscle myosin was 2.24 × 105 and the second virial coefficient was 7.6 × 10-4 ml/g. The values described above are in good agreement with those reported for rabbit skeletal myosin with ammonium sulfate fractionation. The molecular dimension of the molecule is estimated as the value for an axial ratio of 100, assuming a rigid rod molecular model for this molecule, both the thermodynamical and hydrodynamical treatment being in a good agreement with this estimation.
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  • 32
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    Biopolymers 7 (1969) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 33
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    Biopolymers 7 (1969), S. 433-434 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No. Abstract
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  • 34
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enthalpy change accompanying the double helix-coil transition of polyriboadenylic acid (poly A) in aqueous solution has been measured optically and calorimetrically in the pH range 5.7-4.5. The course of this cooperative transition was followed optically by measuring changes in ultraviolet absorption as a function of temperature at different pH values, and calorimetrically by determining the heat capacity of the solution through the transition region. From the latter measurements, the enthalpy of transition was calculated. It is shown, that ΔH is dependent on pH as it is expected from the influence of protonation of the double helix of poly A.
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  • 35
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    Biopolymers 7 (1969), S. 453-458 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction between ionizable carboxyl groups and the conformation of poly-(glutamic acid) (PGA) in aqueous solution were investigated by the mechanical method. The dynamic rigidity of the PGA solution has a maximum value at the pH corresponding to about 50% neutralization point. This may be due to establishing of a maximum attractive force by proton/charge fluctuation between ionizable carboxyl groups at that pH. The dynamic viscosity has a sharp change in the region of pH 5.5-6.5. It is suggested that this behavior is due to the helix-coil transition.
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  • 36
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    Biopolymers 7 (1969), S. 447-452 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By use of D2O we found that the shortening of the longitudinal proton relaxation time which occurs in the investigated aqueous yeast DNA solutions (≦ 2.4% with 2% protein) was not based on a hydration effect, but was caused by magnetic impurities only. An estimate shows that the mobility of the hydrated water molecules is reduced by less than two orders of magnitude in comparison with the free water molecules.
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  • 37
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    Biopolymers 7 (1969), S. 435-445 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general approach to the determination of relative stability of any pair of con-formational states of biological macromolecules or their complexes (in particular, to the determination of relative stability of native and disordered states of the macromolecule) has been suggested. For determining the free energy difference of the two states under the conditions when one of them is considerably more advantageous than the other, it is necessary for the macromolecule to be influenced by the transforming agent which levels free energies of both the conformational states, and to determine the external parameter derivative of the free energy difference in the region of the conformational transition induced by the change in this parameter. If the character of the dependence of this derivative on the external parameter (temperature, solvent composition, etc.) is known, then this allows the determination of the free energy difference of the two states under the conditions considered, even including conditions far from the transition region. The value of the derivative of the free energy difference in the transition region in many cases can be measured directly (in particular, when using calorimetry), while in cases when a direct measurement of the derivative is impossible, it can often he estimated experimentally from the steepness of the conformational transition. The methods of this estimation and also a possible character of the change of the considered derivative during variation of the external parameter are considered for the case when the transforming agent is one of the components of the solvent and, consequently, the derivative of the free energy difference is equal to the difference of number of molecules of this component hound with the macromolecule in two conformational states.
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  • 38
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    Biopolymers 7 (1969), S. 459-474 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Wool-water systems, at water contents above a threshold value of 22.7 g of water per 100 g of wool keratin, yielded curves of specific heat against temperature showing peaks that are ascribed to the fusion of the absorbed water. Integral and incremental heats of fusion were obtained. Integral heats increase as the square of the water content above the threshold, and incremental heats follow a linear relationship. The incremental heat reaches a value of 55 cal/absorbed water, at the saturation water content, at 0°C of 33.9 g of water per 100 g of keratin. The state of the absorbed water is discussed. Clustering of water molecules takes place only above the threshold water content.
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  • 39
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    Biopolymers 8 (1969), S. 173-179 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The laser-excited Raman spectra have been obtained of poly-L-proline in the solid and aqueous solution. In the solid state, the Raman spectra are of the form II which is the left-handed helical form with the peptide bonds in the trans configuration. Dissolution of this form in water produced only minor changes in the Raman spectra. The differences in frequencies produced by dissolving the polymer are associated with vibrational modes of the pyrrolidine ring as indicated by comparison with the Raman spectrum of L-proline. The similarity of the Raman spectra dictates that, the conformations of poly-L-proline chain are similar in the solid and aqueous solution.
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  • 40
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    Biopolymers 8 (1969), S. 181-185 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A comparative study on sonicated calf thymus DNA was made by using electron microscopy and sedimentation methods. The length distribution, established by electron microscopy by using Kleinschmidt's technique, is related to the sedimentation curve obtained with the same solution. The relation permits a determination of the sedimentation constant corresponding to a given length up to 8000 Å and vice versa.
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  • 41
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    Biopolymers 8 (1969), S. 199-216 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The π-electron polarizability of conjugated base molecules such as uracil and adenine are calculated semiempirically by using molecular orbital theories. The Hüekel method and the self-consistent-field (SCF) theory are used in the present calculation. The theoretical values obtained by the Hüekel method are consistently larger than the experimental results. The values obtained by the SCF theory are in good agreement with observed values. It is clearly demonstrated that the SCF method is better than the Hükel method for the calculation of polarizability. The polarizability of the adenine-uracil pair is calculated as the sum of the polarizabilities of adenine and uracil and also calculated by solving the eigenvalue problem for the A-U pair as an entity. The second method gives considerably larger polarizability than the first method. Discussions are presented and it is demonstrated that the second method is the correct way to calculate the polarizability of the A-U pair.
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  • 42
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reversibility of the thermal denaturation of a low-sulfur fraction of solubilized wool keratin (SCMKA) has been studied under a variety of conditions of time, protein concentration, and pH. Two types of irreversibility for the transition have been encountered. One of these is associated with an aggregation of the protein on denaturation to give a product which may contain elements of a β conformation. This type of irreversibility is favored by high protein concentration, and the original conformation may in fact be regained if the aggregated structure is broken down by a solvent such as 8M urea and the urea subsequently removed by dialysis. The other type of irreversibility appears to be due to racemization of the protein. It does not seem to be dependent on protein concentration and is apparent only at temperatures beyond the actual transition range (∼40-65°C) at pH values below 11, At pH 12, however, racemization appears to proceed slowly even at 4°C. The thermal transition at pH 9 and pH 10 has been shown to be multistage in nature. Over the pH range 9-12 there is a progressive decrease in thermal stability with increase of pH. Addition of NaCl at pH 10 leads to an increase in thermal stability of the molecule.
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  • 43
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    Biopolymers 8 (1969), S. 217-235 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report studies of the optical properties of the proflavine-DNA complex, using absorbance and circular dichroism spectroscopy. From comparison of the absorption spectra of proflavine complexed with calf thymus and T2 DNA, we conclude that stacking of the dyes external to the double helix is comparatively much weaker with T2 DXA, probably because of its glucosylation. Several sources are found for the circular dichroism induced in proflavine when it is complexed with DNA. There is a relatively weak circular dichroism induced when the dye is infinitely dilute on the DNA lattice; this presumably arises from the environmental asymmetry of the binding site. Stronger circular dichroism effects are induced by interaction of intercalated and stacked dyes; studies with T2 DNA, for which stacking seems to be blocked, permit a tentative resolution of effects due to the two modes of binding. One recurring theme of these studies is the observation that the optical properties are quite dependent on environment. The most dramatic example is a strong variation with salt concentration of the amplitude of the circular dichroism induced in the isolated (intercalated) monomer by the surrounding DNA. This suggests that the structure of the intercalated complex is quite sensitive to external conditions.
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  • 44
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of n-butanol, benzyl alcohol, and trifluoroethanol to polyproline I (all peptide bonds in cis configuration) and II (all peptide bonds in trans configuration) has been demonstrated. It was found by infrared spectroscopy that hydrogen bonds are formed between the CO groups of the polymer and the OH groups of the alcohols. Their strength increases from n-butanol via benzyl alcohol to trifluoroethanol. The binding of benzyl alcohol could also be followed by optical rotatory dispersion due to the fact that the electronic transitions of the benzyl ring are rendered optically active by the binding to the polymer.
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  • 45
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    Biopolymers 8 (1969), S. 259-274 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The statistical mechanics of the effect of a small number of randomly occurring defects on the melting of a polypeptide chain is developed by using a perturbation of Boltzmann factors technique. The method is illustrated by an example where a second-component impurity contributes more to the energy of the hydrogen-bonded superstructure of the polypeptide chain than does the dominant amino acid residue, resulting in the overall destabilization of the helical conformation.
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  • 46
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    Biopolymers 8 (1969), S. 275-287 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Biological membranes consist mainly of lipids and proteins. At present, the structure of the lipid phase appears to be established, but hypotheses on the molecular organization of the protein are difficult to support. Thus the deformation behavior of whole human erythrocyte ghosts, ghosts after the selective removal of lipids and ghosts stripped of lipids as well as nonlipid components have been examined in the hope of securing indirect information on the organization of the protein. It has been found that large localized deformations result in partial membrane failure and long uniformly wide fibrils, frequently in excess of 3000 Å, are drawn across the rupture. These data are interpreted in terms of currently favored membrane models and the possibility of a fibrous membrane framework consisting predominantly of protein is reviewed. The behavior of the membrane in its various stages of extraction is compared and contrasted to that of synthetic polymer films of known organization.
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  • 47
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    Biopolymers 8 (1969), S. 247-257 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermally induced conformational changes of poly-N5-(3-hydroxypropyl)-L-glutamine in water and in methanol-water (3:7 v/v) have been analyzed in terms of the Lifson-Roig theory. The transitions in both solvents can be described by using v = 0.017. The thermodynamic parameters for the random coil-to-helix transition of one amino acid residue at room temperature were found to be: in water, ΔH = - 130 cal/mole and ΔS = - 0.45 e.u.; in methanol-water (3:7 v/v), ΔH = - 170 cal mole and ΔS = - 0.45 e.u. The size distribution of helical segments is broad, and the results of numerical calculations are presented for three degrees of polymerization (DP = 100, 300, and 750).
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  • 48
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    Biopolymers 8 (1969), S. 289-292 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 49
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    Biopolymers 8 (1969), S. 293-295 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 50
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    Biopolymers 8 (1969), S. 297-299 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 51
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    Biopolymers 8 (1969), S. 303-304 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 52
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    Biopolymers 8 (1969), S. 301-301 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 53
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    Biopolymers 8 (1969), S. 304-304 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 54
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    Biopolymers 8 (1969) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 55
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    Biopolymers 7 (1969), S. 595-610 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclic dipeptide, L-alanylglycyl anhydride, has been studied by optical rotatory dispersion; both L-alanylglycyl anhydride and the lactam, L-3-aminopyrrolidin-2-one, have been studied by circular dichroism. In hydroxylic solvents the circular dichroism spectra of 3-aminopyrrolidin-2-one can be attributed to an n-π* transition near 220 mμ and a π-π* transition near 190 mμ. In these solvents the optical activity of L-alanylglycyl anhydride can be explained as being due to contributions of n-π* transitions and a split π-π* transition. In acetonitrile, however, the circular dichroism spectrum of 3-aminopyrrolidin-2-one shows an additional apparent minimum near 200 mμ. The CD spectrum of the dipeptide is also quite distinctive in this solvent. The possible nature of the band at 200 mμ and the implications of these findings are discussed.
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  • 56
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    Biopolymers 7 (1969), S. 619-623 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 57
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    Biopolymers 7 (1969) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 58
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 59
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    Biopolymers 7 (1969), S. 627-648 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flow birefringence, extinction angles, and intrinsic viscosity have been determined at low velocity gradients for a complex of T2 bacteriophage DNA and methylated serum albumin prepared in dilute solution to a stoichiometry of approximately 90 proteins per DNA molecule. Comparative data upon equivalent solutions of pure uncomplexed T2 DNA are also presented, and these data are completely in accord with the results of previous study. The experimental data are interpreted in terms of current dynamical theory and indicate that the complex has an essentially linear chain structure, consisting of approximately two DNA molecules, which is hydrodynamically indistinguishable from the pure DNA and that extensive internal or intramolecular binding in the complex does not occur. Although interpretation of the results is hampered by an apparent moderate degree of polydispersity in the complex preparations and by relatively large shear extrapolations, the data for both DNA and the complex are substantially in accord with dynamical theory for a nondraining bead subchain model having high kinetic segmental rigidity.
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  • 60
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    Biopolymers 7 (1969), S. 649-658 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Far-infrared spectra in the region from 700 to 60 cm-1 have been measured for the α-helix structures of poly(L-α-amino-n-butyric acid), poly-L-norvaline, poly-L-norleucine, and poly-L-leucine and for the β-form structures of poly(L-α-amino-n-butyric acid), poly-L-valine, poly(DL-amino-n-butyric acid), poly-DL-norvaline, and poly-DL-norleucine. The changes of the spectra on N-deuteration have been measured in the region between 700 and 400 cm-1. It is concluded that, the α-helix has characteristic bauds near 690, 650, 610, 380, 150, and 100 cm-1, and that the β-form has characteristic bands near 700, 240, and 120 cm-1. The main-chain vibrations in the region from 600 to 200 cm-1 are strongly coupled with the side-chain deformation vibrations.
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  • 61
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    Biopolymers 7 (1969), S. 681-693 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Single-strand breaks (ssb) in opposite strands of DNA can be sufficiently near that a double-strand break (dsb) results. A theory is presented by which the maximum number h of base pairs which cannot prevent double-strand breakage can be determined from the rates of production of ssb and dsb. The assumptions required to derive the necessary equations as well as the range of validity of the equations are discussed in detail. In the experiments ssb and dsb were produced by x-irradiation in buffers which do not eliminate indirect effects and were measured by analytical ultracentrifugation. Values of h have been determined in low and high ionic strength and in low ionic strength over a range of temperatures. The values, 2.64 and 15.8, were obtained for high and low ionic strength, respectively.
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  • 62
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    Biopolymers 7 (1969), S. 695-705 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nature of a specific association between acriflavine and cellular DNA was investigated by subjecting the DNA of intact cells to denaturation, ultraviolet radiation, and base analog substitution. The predictable modifications of DNA structure were then correlated with the quantitative alterations in dye adsorption by the cells. It was concluded that, under experimental conditions of limited dye availability, the bonding of dye was restricted to sites of highest bonding affinity. These were shown to be situated between adjacent thymine molecules on a single strand of DNA. The 5-methyl groups of thymine may endow the bond with its specificity.
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  • 63
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    Biopolymers 7 (1969), S. 659-670 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The theory of polyelectrolyte solution of Alexandrowicz: and Katchalsky is used to calculate the electrostatic potential of single stranded polynucleotides for different ionic strength. We have considered the potential of double stranded DNA as the superposition of the different potentials produced by each chain, provided the average distance between the strands is higher than an ionic strength-dependent parameter b. For ionic strength lower than 5 × 10-2M, the assumption is no longer valid, and a cylindrical model with a uniform charge density must be used. The continuity between the two models was tested, and thus we can calculate the electrical potential at the vicinity of a phosphate group in the whole range of ionic-strength where the double helix is stable. It was therefore possible to determine the theoretical number of ions bound electrostatically to DNA and we found an increase of ion binding with a decrease of ionic strength. Such a model was further applied to the change of specific volume in different salt solutions. Comparison is made with recent pycnometric data on Na- and Cs- salts of DNA. Agreement is good in the case of Cs+, but for Na+, cation binding is likely to be accompanied by a change of the hydration of DNA, which depends on ionic strength. With the same model we can see easily the ion-trapping properties of DNA which play an important role in any formation of complex between heavy ions and bases.
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  • 64
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    Biopolymers 7 (1969), S. 671-680 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preferential adsorption of cations occurs in the solvated shell surrounding polyanions, especially polynucleotides and nucleic acids. The solvation parameter Γ is determined from sedimentation coefficients which are considered as pienometric determinations of the specific volume of the sample. By comparing two identical concentrations (0.1M) of monovalent salts, NaCl and CsCl, and using the model of DNA described in the preceding paper, one can relate the ratio SCs/SNa to solvation parameters ΓCs, and ΓNa.On the other hand, Γ can be related to the difference of energy W, between cation and water, to be extracted from the solution and placed in the vicinity of the polyanion. One finds generally a preferential solvation of the polarizable caesium ion by means of London-van der Waals interactions with bases. With reasonable assumptions, an estimate of W can be made, and the predicted value of Γ can be compared to the experimental one. An average of six sites is found around each base in a single-stranded polymer, but-only one in the double-stranded structure. The amount of secondary structure can thus be estimated from the simple measurement of the ratio of two sediment constants.
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  • 65
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 171-182 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To clarify the deformation mechanism in polyblends of polypropylene with ethylene-propylene rubber having different compositions, simultaneous measurements of the infrared dichroism with stress and strain under a constant rate of strain of 1.64%/min have been carried out. The orientation function of the crystallographic c axis of polypropylene in the blends has been obtained as a function of strain ranging from 0 to 20% and of polypropylene content ranging from 0.3 to 1.0. These results have been compared with the temperature dependences of the dynamic Young's modulus and of the loss modulus, as well as of stress-strain curves for the same blends. The modulus data analyzed by Kerner's equation reveal the occurrence of phase inversion at polypropylene contents higher than about 0.5, and this is supported by the infrared dichroism data. The strong effect of quenching on crystalline structure and mechanical properties of pure polypropylene has also been elucidated.
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  • 66
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 183-200 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equipment and methods have been developed which allow photomicrographic determination of the stress-strain properties of the individual craze. Serial cyclic tensile tests on polycarbonate crazes are described. Under stress the typical dry polycarbonate craze thickens solely by straining; no adjacent polymer of normal density is converted to craze material. The craze exhibits a yield stress followed by a recoverable flow to roughly 40-50% strain at 6000-8000 psi. On return to zero stress the craze exhibits creep recovery at a decelerating rate. The yield stress and loss factor of each cycle decrease with increasing initial strain and cycles initiating at 50% strain or more show completely Hookean behavior. Creep recovery results in recovery of yield stress and loss factor also. Craze tensile behavior is suggested to be essentially an extension of the craze formation process. Decrease in elastic modulus and yield stress with increasing strain are rationalized in terms of strain-produced decrease in density and resultant increase in stress concentration factor on the microscopic polymer elements of the craze. Polymer surface tension and the large internal specific surface area of the craze are suggested to be important factors in the large creep recovery rates of the craze.
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  • 67
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 241-248 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method of determining distributions of the degree of polymerization by means of probability theory is derived. This method, based on Kolmogorov's forward differential equation, is illustrated by application to two familiar kinetic schemes and is used to derive the distribution of degree of polymerization for free-radical polymerization with diffusion-controlled termination.
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  • 68
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 271-278 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of birefringence of a polymer film upon its photographic light-scattering pattern is considered for the case of a single, anisotropic, two-dimensional spherulite imbedded in a birefringent matrix. It is shown that for the case of a polarizer and analyzer crossed at +45° and -45° to the analyzer, the scattering pattern is modified in a manner agreeing with experimental observation.
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  • 69
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 285-295 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Osmotic-pressure, viscosity, and light-scattering measurements have been carried out on dilute solutions of poly-N-vinylcarbazole fractions (4 〈 10-4M 〈 230) in toluene, dioxane, and benzene. The theta temperature for poly-N-vinylcarbazole in toluene solutions has been found to be 37 ± 1°C. The intrinsic viscosity of poly-N-vinylcarbazole in toluene at 37°C is represented by [η]θ = 76.2 × 10-3M̄n0.50. Values of the characteristic ratios (〈L2〉0/M)1/2 and σ = (〈L2〉0/〈L2〉0f)1/2 have been obtained as 633 × 10-11 and 2.85, respectively. It appears that the large σ value is due to the steric repulsion between large side groups.
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  • 70
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical relaxation data as a function of temperature (ca. 1 Hz) have been obtained for several samples of isotactic polypropylene crystallized from the melt, which exhibit both α and β forms as well as varying degrees of lamella orientation. The samples ranged in morphology from an unoriented sample showing only the α form to one highly oriented having approximately 90 per cent the β form. Results for the logarithmic decrement Δ and loss modulus G″ are that the low temperature (ca. -75°C) and glass temperature (ca. 0°C) relaxations show little or no sensitivity to orientation in the α form, but that the intensity of the two processes is different in the α form than in the β form for samples of nearly equal overall per cent crystallinity. In both Δ and G″, the low-temperature peak decreased and the glass temperature peak increased in intensity as the fraction of β form crystallinity present increased. Data for the high-temperature relaxation (ca. 80°C) indicate a dependence upon orientation and/or crystal form in addition to a dependence upon per cent crystallinity.
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  • 71
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 411-422 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscometric behavior of linear polycaprolactam has been studied in the absence of the electroviscous effect in aqueous solvents containing 85% and 64.5% formic acid and in trifluoroethanol, as a function of temperature and also under unperturbed conditions. Results are discussed in terms of the existing theories; in particular, the negative temperature coefficient of the intrinsic viscosity arises only from the variation of the expansion coefficient, the molecule in the unperturbed state being a normal random coil. The absence of aggregation and draining effects in the above solvents has been varified.
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  • 72
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 463-473 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymers of poly(N-acyl and N-aroyl aziridines) were studied by x-ray diffraction. All the crystalline polymers studied have a triclinic unit cell with two monomer units per unit cell. The a and c (fiber direction) parameters (4.9 and 6.5 A, respectively) are essentially the same for all the cells. The b parameter for the N-acyl polymers, however, increases steadily by a factor of 2 A per methylene group added to the lateral chains. The densities calculated for the unit cells are in agreement with the experimental values obtained. The most probable structure is one in which the molecules assume a planar configuration with the main chain not fully extended. The lateral groups are tilted from the c axis by an angle of 54° in a parallel configuration and alternate on each side of the main chain. This permits these lateral groups to assume packing similar to that of polyethylene. A brief description of the techniques used in this interpretation is included.
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  • 73
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Results from characterization of melt-polymerized nylon 66 by various solution property measurements are reported and employed in analysis of typical molecular weight and compositional distributions for these systems. Critical attention is paid to application of standard procedures including light scattering, viscosity, membrane osmometry and other colligative property measurements in arriving at satisfactory specification of polymer molecular weight averages. Particular consideration is given to polymers extending appreciably beyond the lower and higher limits in molecular weight normally encountered. The conclusions drawn are: (1) in the range of number-average molecular weights less than about 25 000, nylon 66 as ordinarily prepared by melt condensation consists principally of linear species approximating the “most probable” distribution; (2) small amounts of cyclic oligomers are present in all samples: (3) increase in the extent of the melt polycondensation to progressively higher stages is accompanied by secondary reactions and the formation of branched components terminating ultimately in crosslinked, insoluble gels. Intrinsic viscosity-molecular weight relationships in seven solvents, applicable to nylon polymers meeting the requirements of (1) above, are derived.
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  • 74
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 57-76 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For an infinitely repeated regular polymer chain structure the only vibrations which are optically active are those in which the phase of the motion is the same in each unit (the factor-group modes). Frequencies for which the phase difference is nonzero are optically inactive but can become activated by the presence of defects in the chain. Such defects would normally be chemical impurities or conformational irregularities in the chain. A simple theory is developed which shows that for a dilute system of defects the major characteristics determining possible activation of the nonfactor-group modes are: (1) the strength of the coupling between the defect vibration and the vibrations of the neighboring chain, and (2) whether or not the natural frequency of the defect vibration lies inside a lattice band of the regular chain. An analysis of the low- and high-frequency regions of the spectrum of low-density polyethylene, based on the above considerations, indicates that several features of the spectrum can be associated with defect-induced absorption. A similar explanation can account for certain intensity changes in the C—Cl stretching region of syndiotactic poly(vinyl chloroide) when this polymer is submitted to mechanical treatment.
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  • 75
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general description is given for relations among the optical quantities obtained from fluorescence polarization measurements on bulk polymer stained by fluorescent groups: the moments of distribution of orientations of the fluorescent groups, and those of the structural units of the polymer (chain segments) on which the groups are adsorbed. Two assumptions as to the biaxial symmetry of the bulk polymer and the cylindrical symmetry of the optical anisotropy of the fluorescent element, both for the absorption and emission processes, reduce the intensities of the polarized fluorescence to a 3 × 3 matrix L which is asymmetric (Lij ≠ Lji), as has frequently been observed in experiments. The components of the L matrix are related to those of the J matrix which is so defined as to describe the fourth moments of the distribution of orientations of the structural units on the basis of a random distribution of the rotational angle of the unit about the segment axis. It is found that the use of the method of fluorescence polarization combined with absorption dichroism and/or emission gives the values of the optical anisotropy ratios of the fluorescent unit, and that the effects of the thermal agitation of the structural unit can be separated from the moments of the orientation distribution for the simplest case.
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  • 76
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 747-748 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 77
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 753-762 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Eight epoxy-diamine networks have been formed, diamines with 2 to 12 methylene groups being used as curing agents. Dynamic mechanical tests revealed four transition regions in the dynamic loss modulus/temperature relationship. Two possible explanations for the relaxation of the glycidyl portion of the structure are proposed. One of the relaxations could be due to the breakdown of hydrogen bonds through the hydroxyl and ether groups. The second could be ascribed to the relaxation of the unbonded glycidyl groups or a second relaxation of the glycidyl groups after the breakdown of the hydrogen bonds.
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  • 78
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 783-794 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Previous theoretical calculations of elastic constants for cellulose based on force constants for bond stretching and bending of valence angles have yielded axial stiffness values admittedly too low. The present analysis accounts for a hitherto unexamined geometrical effect associated with deformation of interchain hydrogen bonds. To do this, most primary bond deformations are neglected so the resulting calculation gives an upper bound for the axial stiffness. By using two different sets of hydrogen bond force constants, values of 24.6 and 31.9 × 1011 dyne/cm2 were obtained for Young's modulus in the chain direction. These values are very much larger than earlier calculations and experimental determinations from cellulosic fibers, indicating both the importance of the effect considered here and the likelihood of an exact analysis yielding an acceptable result.
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  • 79
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 845-853 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational energy contribution (ΔUconf) to the heat of solution in polymer-solvent systems is presented and discussed in connection with chain conformational properties. In particular, ΔUconf has been discussed in terms of various possible mechanisms of coil deformation.
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  • 80
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 889-896 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is demonstrated that in a filled polymer the thermal stresses resulting from the difference in the thermal expansion coefficients of the filler and the polymer have significant effect on the apparent coefficient of thermal expansion of the composite. A model is constructed to aid the thermal stress analysis, and the results are found to agree well with the experimental data obtained from other sources. An expression for the apparent densities of filled polymers is also obtained but the agreement between the present prediction with an existing test result is found to be only qualitative.
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  • 81
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 947-962 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diffusion coefficients and solubilities of methane in polyisobutylene have been measured at four temperatures between 102 and 188°C. in the pressure range 23-341 atm. Diffusion coefficients extrapolated to atmospheric pressure range from 1.72 × 10-6 cm.2/sec. at 102°C. to 1.5 × 10-5 cm.2/sec. at 188°C. corresponding to an activation energy for diffusion of 8.7 ± 0.4 kcal./mole. Solubilities are small, about one molecule of methane for every forty carbon atoms in the polyisobutylene at 300 atm. partial pressure of methane. Solubilities vary little with temperature, but show an apparent minimum between 127 and 188°C. With improved methods of data analysis, diffusion coefficients and solubilities have been recalculated from previously reported studies on nitrogen in branched polyethylene and methane in branched polyethylene, linear polyethylene, and polystyrene. Recalculated diffusion coefficients are essentially the same as those reported previously, but the recalculated solubilities are decreased from 2 to 30%. The solubilities of all five systems show strong deviations from Henry's law, i.e., increases in partial pressure of methane and nitrogen with respect to solubility exceed linearity. The partial pressure (or fugacity) - solubility data may be interpreted in terms of a sorption model in which sorbed molecules are accommodated in widely dispersed, unoccupied volumes or sites in the polymer. An almost equivalent, solution model in which the first sorbed molecules to enter the polymer are accommodated to a large extent in existing volumes in the polymer, with successively sorbed molecules swelling the polymer to a greater extent (i.e., partial molal volume of sorbed molecules, V1, increasing with concentration) can also account for these data.
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  • 82
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1021-1031 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The discrepancy between the values of the anisotropy of methylene groups determined from crystal refractive indices, stress-optical data, and gas and liquid light-scattering depolarization is explained on the basis of the effect of the internal field on the polarizability of the isolated molecule. The internal field may arise from intermolecular or intramolecular interactions which depend upon molecular conformation and state of aggregation. A simple continuum calculation based upon an extension of the calculation of the Lorenz-Lorentz field is shown capable of accounting for the discrepancy.
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  • 83
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1059-1073 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nylon 66 films exhibiting form I melting behavior show the γ mechanical relaxation at -140°C. Samples which have form II melting behavior do not show this relaxation. The γ relaxation disappears when material having form I behavior is converted to material having form II behavior by annealing or by cold drawing. The form I and form II types of melting behavior are also found in poly(ethylene terephthalate); the interconversions and thermal behavior of the forms are analogous to the nylon 66 case. In poly(ethylene terephthalate), the β relaxation at -40 to -60°C is present only when form I melting behavior is found. Conversion to form II melting behavior by annealing or drawing (80°C) again causes the relaxation to disappear. No β relaxation was found in amorphous polymer. The γ dispersion in nylon 66 and the β dispersion in poly(ethylene terephthalate) can therefore be associated with the crystalline structure responsible for form I melting behavior. Form I melting behavior has been associated with foldedchain crystals based on previous work. It is therefore postulated that the γ dispersion in nylon 66 and the β dispersion in poly(ethylene terephthalate) are associated with motions in the chain folds. This assignment is not inconsistent with the change in the γ dispersion of nylon 66 with the number of backbone CH2 units, since these will affect the fold structure.
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  • 84
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1116-1118 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 85
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1151-1163 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strength-limiting process in the fracture of semicrystalline fibers and highly oriented films is the rupture of tie molecules connecting the folded chain lamellae in the machine direction. This view is supported by the data on stress and temperature dependence of lifetime of fibers under load and on radical formation during the fracture experiment. The observed tensile strength, however, is about 10 times smaller and the number of fractured chains between 100 and 1000 times larger than expected on the basis of the known number of tie molecules in the fracture plane. This discrepancy is a consequence of the inhomogeneity of the micromorphology of fiber structure, which causes a much larger stress concentration on the most unfavorably located tie molecules than the average value one would expect in the case of perfectly uniform stress distribution on identical tie molecules. The fluctuation of amorphous layer thickness, of number and length of tie molecules, produces such a high stress concentration on some tie molecules throughout the sample that they rupture long before the average stress concentration is sufficient for chain fracture. By accumulation of damage caused by gradual chain rupture the weakening of the sample locally proceeds so far that at the maximum damage concentration, microcracks start to form, and the fiber breaks.
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  • 86
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 525-536 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic shear behavior of four highly amorphous polymers in the unstretched and stretched states (draw ratios 3:1 to 6:1) was investigated with a torsion pendulum at temperatures from 4.2°K to 180-300°K and frequencies from 0.4 to 3.2 cps. The polymers studied were polystyrene, poly(vinyl acetate), poly(vinyl propionate), and poly(isobutyl vinyl ether). Previously unreported loss maxima were found at 48°K (1.5 cps) and 149°K (1.3 cps) for poly(vinyl proplonate), at 10°K (1.0 cps) for poly(vinyl acetate) and at 9°K (1.6 cps) for poly(isobutyl vinyl ether). Uniaxial orientation increased the shear storage modulus G, measured with the torsion axis parallel to the stretch direction and caused changes in the loss peaks which depended on the polymer material studied.
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  • 87
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 551-561 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle x-ray scattering studies were made on bulk-crystallized samples and annealed oriented films of TMPS. The temperature dependence of the small-angle scattering was determined over a range of annealing conditions. The effect of sample molecular weight on the small-angle peaks was also studied. The peak intensity, measured at room temperature after annealing, was strongly dependent on the annealing conditions. The position of the peak gradually moved to smaller angles (larger d spacings) as the annealing temperature was raised. Surface free energies were deduced from the melting point dependence of the crystallite size. This surface energy was found to increase with molecular weight in accord with values deduced for spherulite growth rate-temperature dependence.
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  • 88
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 593-600 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model is proposed to account for the regular twisting of radial ribbons in certain polymer spherulites. The model assumes that the ribbons have crystallographically regular fold surfaces and that growth of the ribbons is nucleation-controlled. The model leads directly to a possible mechanism of spherulitic growth in some polymers.
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  • 89
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 659-666 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A specimen of linear polyethylene was subjected to isothermal secondary crystallization at a series of temperatures below the primary isothermal crystallization temperature, the melting and primary crystallization stages being held constant throughout the investigation. Dilatometric measurements exhibit an S-character at low values of undercooling Tp - Ts, where Tp and Ts are, respectively, the primary and secondary crystallization temperatures; at larger undercoolings, however, an initial very rapid crystallization is followed by a very slow stage. When corrected for thermal contraction of the polymer, the net degree of secondary transformation is seen to peak at a temperature in the range 109-113°C. The S-character of the isotherms and the peaked temperature variation of degree of transformation lead to the conclusion that a large portion of the secondary crystallization consists of the nucleation and growth of the new crystallites. Johnson-Mehl-Avrami analysis leads to a model of heterogeneous nucleation within the remaining amorphous zones, followed by one-dimensional, diffusion-controlled growth.
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  • 90
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 675-685 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strength and extensibility of an unfilled styrene-butadiene rubber vulcanizate were determined in constrained biaxial tension (essentially pure shear) by stretching thinwalled cylindrical specimens in the axial direction with an Instron tester while gas pressure was admitted to maintain constant the outside diameter of a specimen. The rupture stress, λ1b, and the extension ratio, λ1b, in the axial direction and the rupture stress, σ2b, in the circumferential direction were determined at extension rates from 0.0031 to 3.1 min-1 and temperatures from 25 to 90°C. Rupture data in simple tension were also obtained by testing ring specimens under similar test conditions. The time-temperature shift factor, aT, obtained by superposing rupture data at different temperatures, gives a constant activation energy of 35 kcal. Doubly logarithmic plots were prepared showing the dependence of σ1b/λ1b, σ2b, and λ1b from the biaxial tensile tests and of σb/λb and λb from the simple tensile tests on the temperature-reduced extension rate, \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \lambda a_T $\end{document}. (The quantities σ1b/λ1b, σ2b, and σb/λb are rupture stresses based on the dimensions of undeformed specimens.) At equal values of \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \lambda a_T $\end{document}, the extension ratios λ1b and λb are sensibly identical. The ratios σ1b/σb and σ2b/σb, as well as λbσ2b/σb, were obtained from rupture data read from the composite curves at selected values of \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \lambda a_T $\end{document}. Also, similar ratios were derived from stress data at equal extensions in biaxial and simple tension for 1.25 ≤ λ ≤ 3.0, the range comparable to that in which rupture data were obtained. A consideration of the ratios given by both the rupture and the stress data shows that the von Mises failure criterion is not applicable, although the departure is small except at the larger values of λb.
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  • 91
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 747-747 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 92
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 750-750 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 93
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 775-782 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A statistical model for the stereospecific polymerization of vinly monomers on Ziegler-Natta catalytic systems is presented. The basic assumptions of the model are: (a) the catalytic centers are asymmetric, so that at a given catalytic center the monomer CH2=CHR is inserted into the chain with two different rates according to the two different configurations of the opening carbon atom having the R group; (b) the insertion of a monomeric unit in the growing chain is affected also by interactions with the previous monomeric unit. Isotactic, syndiotactic, atatic, or stereoblock polymers are obtained according to the relative values of the two energy parameters expressing these two effects.
    Additional Material: 1 Ill.
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  • 94
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 821-827 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A specimen of linear polyethylene was subjected to isothermal secondary crystallization at a series of temperatures below the primary isothermal crystallization temperature, the melting and primary crystallization stages being held constant throughout the investigation. Dilatometric measurements exhibit an S-character at low values of undercooling Tp - Ts, where Tp and Ts are, respectively, the primary and secondary crystallization temperatures, whereas at larger undercooling, an initial very rapid crystallization is followed by a very slow stage. When corrected for thermal contraction of the polymer, the net degree of secondary transformation is seen to peak at a temperature about 5°C below Tp. The S-character of the isotherms and the peaked temperature variation of degree of transformation lead to the conclusion that a large portion of the secondary crystallization consists of the nucleation and growth of the new crystallites. Johnson-Mehl-Avrami analysis leads to a model of heterogeneous nucleation within the remaining amorphous zones, followed by one-dimensional, diffusion-controlled growth.
    Additional Material: 3 Ill.
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  • 95
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 855-866 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heats of solution (ΔHexp) in solvents of increasing thermodynamic power have been measured for four polymers: polystyrene (PS), poly(vinyl acetate) (PVAc), polyisobutylene (PIB) and polydimethylsiloxane (PDMS). After subtraction from ΔHexp of an interaction term (calculated by the Hildebrand treatment based on solubility parameters) and the excess volume term, the quantity remaining is interpreted as the conformational energy contribution (ΔUconf) to the heat of solution. ΔUconf appears to correlate well with some basic conformational properties of the chain, such as the sign of the temperature coefficient of unperturbed dimensions derived from solution properties, and shows a monotonic behavior with α, the expansion coefficient of the polymer coil in the final solution. Numerical values of ΔUconf, at least for those cases in which polymer solubility parameters are known with some certainty, are much larger than those evaluated from rubber elasticity experiments (through the experimentally accessible value of the energy component of the force of retraction im simple elongation).
    Additional Material: 5 Ill.
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  • 96
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1101-1109 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyvinylpyridine of molecular weight 0.77 × 106 was crosslinked by 2.5, 5, and 10% BrCH2C6H4CO(CH2)8COC6H4CH2Br and by 10% ClCH2C6H4CH2Cl; quaternization of the gel was completed with n-butyl bromide. Swelling ratios in aqueous solutions of lithium, sodium, and 4-isopropyl-N-n-butylpyridinium bromide and in methanolic lithium bromide were determined. Selectivity increased in the sequence Li+ 〈Na+ 〈PrN+-C5H5. The Flory parameter χ1, which measures interaction between solvent and polymer, decreased from 1.5 kT to nearly zero with increasing density of crosslinks in the aqueous solutions, and from 3 kT to 0.5 kT in the methanol solutions. The inverse proportionality of q2/3 (q = swelling ratio) to the crosslinking density was approximately verified for swelling of the resins in water, methanol, and dimethylformamide.
    Additional Material: 5 Ill.
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  • 97
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1165-1186 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The proton spin-lattice relaxation times (T1) of linear polyethylenes (PE) of varying morphology were measured as a function of temperature. The T1 of oriented bulkcrystallized and solution-crystallized material was isotropic, in disagreement with calculations based on a sample dipole pair model. Motion in the non-crystalline regions of the samples is shown to be responsible for the T1 minimum occurring around -20°C. The dependence of T1 at the minimum on the long period reinforces the model of an amorphous fraction composed of disordered lamellar surface layers. The temperature of the T1 minimum and the dependence of T1 on the long period imply that the mobility of these amorphous regions is reduced in cold-drawn and solution-crystallized samples. This mobility irreversibly increases with annealing. In highly relaxed samples the motion of a small portion of the disordered regions is almost liquidlike, as indicated by the presence of a second shorter T1.
    Additional Material: 12 Ill.
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  • 98
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 963-981 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structural and steric isomerism of propylene polymers has been estimated on the basis of solution properties as well as infrared and high-resolution nuclear magnetic resonance spectra. Three general types of polypropylenes were prepared: polymers prepared with the cationic catalytic system AlCl3-C2H5Cl, stereoblock polymers obtained by successive extraction from a commercial product and isotactic polymers of low molecular weight obtained by thermal degradation of a highly isotactic polymer followed by hydrogenation with Adam's catalyst in dioxane at 40°C. The characterization of all samples was accomplished by equilibrium ultracentrifugation, vapor-pressure osmometry, viscometry, and gel-permeation chromatography. It is found that the molecular chain of cationically prepared polymer is somewhat branched owing to structural isomerism during polymerization. Isoamyl acetate is found to be a theta solvent for stereo-block as well as for atactic and syndiotactic polymers; the theta temperature is determined as the temperature at which the light-scattering second virial coefficient A2 vanishes. A close correlation is found between the theta temperature and stereoisomerism. The absorbances of the 1154 and 974 cm-1 bands in the infrared spectra decrease with decreasing molecular weight; in addition to the mere existence of alternating CH2 and CH(CH3) groups in the polymer chain, rather long sequences of this type are required for the appearance of these bands. Changes in the absorption band at 997 cm-1 show that chains consisting of over ten isotactically connected monomer units can assume a helical conformation. From the high-resolution NMR spectra of different polypropylenes, including isotactic polymers of low molecular weight, it is found that in estimating the microstructure, account must be taken of the effects of stereoisomerism within tetrads of monomer units on the apparent widths of the methylene proton resonances. If substantial concentrations of several of the possible types of tetrads are present (i.e., if the tactic sequence lengths are quite short), then it is difficult to determine the relative amounts of tactic dyads accurately from the 100 Mcps methylene proton resonances.
    Additional Material: 14 Ill.
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  • 99
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1033-1057 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phenomenon of double melting, as manifested by two characteristic endotherms in the melting region on a differential thermal analysis (DTA) scan, has been studied in nylon 66 and polystyrene as a function of sample treatment by annealing or drawing. A variety of techniques were used in these studies including DTA, x-ray diffraction, electron microscopy, and mechanical testing. It is shown that the two endotherms are not caused by a bimodal crystal size distribution, by recrystallization, by orientation changes, or by phase changes. It is proposed that one endotherm is caused by the melting of foldedchain crystals, while the other is due to the melting of less perfect bundle crystals. This view is well supported by the results, especially by the DTA measurements made at different heating rates. Published data on the thermal behavior of annealed and drawn poly(ethylene terephthalate) and on polyethylene crystallized at various pressures may also be explained on this basis if it is allowed that in polyethylene the chains may be more extended.
    Additional Material: 15 Ill.
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  • 100
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1745-1754 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The yield-stress behavior of two glassy polymers is studied through the glass transition region over a wide range of strain rates. For temperatures below the glass transition temperature, the yield stress behavior could be described as a non-Newtonian flow in agreement with Eyring's theory, if one excepts a narrow range relating to the slowest strain rates. For temperatures above Tg, the yield-stress behavior is still nonlinear but fits the relations based on the concept of free volume.
    Additional Material: 5 Ill.
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