Excluded Volume Effect of Linear Polymer Molecules

Kurata, Michio; Stockmayer, W. H.; Roig, A.

doi:10.1063/1.1731070

Cited by 255 publications

(20 citation statements)

References 24 publications

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“…13 The investigation of the other extreme, i.e., the asymptotic solution for R at large z, has been initiated by Edwards'4, applying the self-consistent field method. Subsequently, this approach has been further investigated by Reiss'5 and others '6' 17 21 22 We note that integro-differential equations have also been derived by the liquid theory approach23 24 As for the derivation of approximate closed expressions for R or , various attempts have been made for many years3. In these the problem has been approached from two starting points.…”

Section: Expansion Factorsmentioning

confidence: 99%

Excluded volume effects and binary cluster integrals in dilute polymer solutions

Yamakawa¹

1972

Pure and Applied Chemistry

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Recent advances in the theory of dilute polymer solutions are critically summarized. The following topics are discussed: theory of the excluded volume effect, including perturbation theory, the asymptotic solution, and approximate treatments: the second virial coefficient: the theory of intrinsic viscosity. especially perturbation theory: comparison of theory with experiment using data recently obtained for monodisperse polystyrenes: methods of determining the binary cluster integral: and simple analysis of the binary cluster integral by a cell-theory approach. INTRODUCTIONThe statistical mechanics of polymer solutions has been for many years one of the active lields of polymer science because of its close relation to molecular characterization. Specifically, since the concept of the excluded volume effect in a polymer chain was introduced by Flory"2 in 1949, there have been a number of significant advances in the study of this effect and the related equilibrium and nonequilibrium properties of dilute polymer solutions. These advances, made during the last two decades, have delineated

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Section: Expansion Factorsmentioning

confidence: 99%

Excluded volume effects and binary cluster integrals in dilute polymer solutions

Yamakawa¹

1972

Pure and Applied Chemistry

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“…(6) vor : a2-1 = C.j(ii)ii bzw. a5-a3 = C.j(I)z, (8) wobei j(E) eine mit wachsendem z abfallende Funktion von ii und C = 134/105 ist *). Hier is t a* der thermische kubische Ausdehnungskoeffizient der Losung.…”

Section: (4) (5)unclassified

Thermodynamisches verhalten, expansionskoeffizient und viskositätszahl von polystyrol in tetrahydrofuran

Schulz

Baumann

1968

Makromol. Chem.

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ZUSAMMENFASSUNG:Streulichtmessungen ergeben, daD Polystyrollosungen in Tetrahydrofuran stark exothermisch sind; der 2. Virialkoeffizient des osmotischen Druckes A2 wird iiberwiegend durch den Enthalpieterm A~, H bestimmt. Der Expansionskoeffizient gehorcht der (a5 -a3)-Beziehung mit der Konstante von STOCKBUYER und die h(E)-Funktion der Gleichung von CASASSA. Die Viskosititszahl [q] wird durch die Gleichung von KURATA und YAMAKAWA erfaBt. Mit den drei Parametern p/M$ KO = f i / M und b/MA (b = hydrodynamischer Durchmesser) lassen sich A2, a, [q] und der Treheitsradius f iiber einen groDen Molekulargewichtsbereich in guter Ubereinstimmung mit den MeDwerten berechnen (vgl. Abb. 3). SUMMARY:Light scattering measurements of solutions of polystyrene in tetrahydrofuran show a strongly exothermal behaviour. The major part of the second virial coefficient A2 is the enthalpie term A23. The expansion coefficient a follows the relation of FLORY, as modified by STOCEMAYER a5 -a3 = 134 z/105 and the h(l)-function complies with the equation of

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“…Moreover, they observed that at 500,000 d [700-800 base pairs (bp)] the double-stranded poly(A) and the DNA had measured relaxation times which were substantially below the value predicted for a rigid rod [~(observed)/~(rigid) = 0. 41 for DNA]. Although these studies were subject to the first two uncertainties mentioned above, they suggest an approach to the study of the flexibility of DNA which would be quite sensitive to small changes in overall configuration.…”

Section: Introductionmentioning

confidence: 99%

Investigation of the flexibility of DNA using transient electric birefringence

1981

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SynopsisIn the preceding article, a Monte Carlo analysis was presented which provides a quantitative numerical relationship between the rotational diffusion coefficients, as measured by the decay of optical anisotropy following an electric field pulse, and the flexibility (persistence length) of short, wormlike chains. In the present article, the results of the foregoing analysis are applied to the observed rates of decay of birefringence for a series of sequenced DNA fragments ranging in size from 104 to 910 base pairs. Under the conditions used in this study, the DNA fragments exist as native, duplex molecules. Furthermore, conditions are defined in which the observed relaxation times are not dependent on DNA concentration, field strength, or the duration of the pulse. It is pointed out that the ionic atmosphere associated with a wormlike polyion does not exert any significant (direct) influence on the rotational diffusion of the polyion and, therefore, that the rotational relaxation times are a true measure of the configurations of the DNA molecules in solution. Moreover, excluded-volume effects are shown not to be significant for the moderately short molecules employed in this study. The major conclusion of this study is that there is no strong ionic strength dependence of the persistence length for ionic strengths above 1 mM and that the persistence length, under conditions where electrostatic contributions are negligible, is approximately 500 A. For ionic strengths significantly lower than 1 mM, electrostatic contributions to the stiffness of DNA become significant.

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Excluded Volume Effect of Linear Polymer Molecules

Cited by 255 publications

References 24 publications

Excluded volume effects and binary cluster integrals in dilute polymer solutions

Excluded volume effects and binary cluster integrals in dilute polymer solutions

Thermodynamisches verhalten, expansionskoeffizient und viskositätszahl von polystyrol in tetrahydrofuran

Investigation of the flexibility of DNA using transient electric birefringence

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