Organometallic Polymers with Transition Metals in the Main Chain.

Among the Various methods for characterizing macromolecules in solution, hydrodynamic techniques play a major role. Since the advent of the ultracentrifuge and the development of viscometric apparatus, sedimentation coefficients and intrinsic viscosities have been extensively used to learn about the size and shape of synthetic and biological polymers. More recently, refined techniques such as quasielastic light scattering, transient electric birefringence and fluorescence anisotropy decay have made it possible to obtain in a simple and rapid way quantitative information of high precision on the translational and rotational brownian dynamics of dissolved macromolecules.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0033583500002080

Hydrodynamic properties of complex, rigid, biological macromolecules: theory and applications.

The formalism for the calculation of translational friction coefficients of symmetric top macromolecules presented in a previous paper [M. M. Tirado and J. Garcia de la Torre, J. Chem. Phys. 71, 2585 (1979)] is here extended to the evaluation of rotational friction and diffusion coefficients. We show how the introduction of symmetry considerations leads to a great reduction of the computational requirements needed to solve the hydrodynamic interaction equations. We also obtain the translation–rotation coupling tensor from which the center of hydrodynamic stress can be obtained. For a rigid ring we have derived analytical solutions that reduce to those obtained by other authors when the unmodified interaction tensor is used. The general formalism is finally applied to the calculation of the rotational diffusion coefficients of circular cylinders modeled as stacks of rings and extrapolated to zero bead size. The resulting values are critically compared with those from earlier studies.

Rotational dynamics of rigid, symmetric top macromolecules. Application to circular cylinders

The hydrodynamic properties of cylindrical (rodlike and discoidal) particles in dilute solution have been computed using the bead-shell model treatment. Previous results [Tirado and Garcia de la Torre, J. Chem. Phys. 71, 2581 (1979); 73, 1993 (1980)] for rods with length-to-diameter ratio p>2 are now extended to short cylinders and disks down to p=0.1. The intrinsic viscosity is obtained for rods and disks, and results are presented for the three rotational relaxation times of a cylindrical particle. The hydrodynamic properties are expressed in forms that have a weak variation with p, and are therefore useful for the analysis of experimental values. We present examples of the determination of the length and diameter of the cylindrical particles, for DNA oligonucleotides and tobacco mosaic virus.

Hydrodynamic properties of rodlike and disklike particles in dilute solution

This article reviews the following solution properties of liquid-crystalline stiff-chain polymers: (1) osmotic pressure and osmotic compressibility, (2) phase behavior involving liquid crystal phase(s), (3) orientational order parameter, (4) translational and rotational diffusion coefficients, (5) zero-shear viscosity, and (6) rheological behavior in the liquid crystal state. Among the related theories, the scaled particle theory is chosen to compare with experimental results for properties (1)–(3), the fuzzy cylinder model theory for properties (4) and (5), and Doi's theory for property (6). In most cases the agreement between experiment and theory is satisfactory, enabling one to predict solution properties from basic molecular parameters. Procedures for data analysis are described in detail.

Concentrated solutions of liquid-crystalline polymers

Wormlike Chains Near the Rod Limit: Translational Friction Coefficient

Dilute-Solution Behavior of a Rigid Polymer, Poly[ trans -bis(tributylphosphine)platinum 1,4-butadiynediyl]

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Masanori Motowoka

Papers

Wormlike Chains Near the Rod Limit: Translational Friction Coefficient

Dilute-Solution Behavior of a Rigid Polymer, Poly[ trans -bis(tributylphosphine)platinum 1,4-butadiynediyl]