Slonitskii S V, Frisman E V, Valeev A D, El'iashevich A M
Mol Biol (Mosk). 1980 May-Jun;14(3):484-95.
On the basis of the excluded-volume effect theory for nonionic polymer molecules developed by Alexandrowicz semi-empirical formulas for calculation of the intrinsic viscosity [eta] of polyelectrolytes of various rigidity are proposed. The expression for the second virial coefficient of gas consisting of cylindrical particles is used for the determination of explicit form of the effective excluded volume of the segment upsilon0. In addition the alteration of Flory's parameter phi (epsilon) by the expansion of a macromolecule, and the alteration of thermodynamic rigidity A of the polyelectrolyte molecule in the range of low ionic strengths mu have been taken into account. All that leads to good agreement between calculated and experimental values of [eta] of polyelectrolytes under consideration, i. e. native and denatured DNA and poly (acrylic acid), in a wide range of mu. The calculated dependence A = A (mu) providing the best agreement between the theoretical and experimental values of [eta], also describes reasonably the experimental dependence A = A (mu) obtained from the macromolecule's optical anisotropy measurements for native DNA or from unperturbed dimensions of the macromolecule, determined on the basis of the Stockmayer and Fixman equation for denatured DNA.
基于Alexandrowicz提出的非离子聚合物分子的排除体积效应理论,提出了计算各种刚性聚电解质特性粘度[η]的半经验公式。由圆柱形颗粒组成的气体的第二维里系数表达式用于确定链段有效排除体积υ0的显式形式。此外,还考虑了大分子膨胀对Flory参数φ(ε)的影响,以及在低离子强度μ范围内聚电解质分子热力学刚性A的变化。所有这些都使得在所考虑的聚电解质(即天然和变性DNA以及聚丙烯酸)的[η]的计算值和实验值之间在很宽的μ范围内取得了良好的一致性。计算得到的依赖关系A = A(μ)使得[η]的理论值和实验值之间达到最佳吻合,同时也合理地描述了通过天然DNA大分子的光学各向异性测量得到的实验依赖关系A = A(μ),或者基于变性DNA的Stockmayer和Fixman方程确定的大分子无扰尺寸得到的实验依赖关系A = A(μ)。