Macromolecular Hydrodynamics and Fractal Structures of the Lignins of Fir Wood and Oat Husks

Abstract

The topological structure of the macromolecules of lignins isolated from oat husk and fir wood was studied by means of macromolecular hydrodynamic methods. The macromolecular properties were analyzed by evaluating the intrinsic viscosity and coefficients of the translational diffusion and the sedimentation velocity of the lignins in dilute dimethylformamide solutions. The average molecular weights (MDη) and polydispersity parameters were calculated based on the results of the fractionation, as follows: Mw = 14.6 × 103, Mn = 9.0, and Mw/Mn = 1.62 for lignins from fir wood and Mw = 14.9 Mn = 13.5 and Mw/Mn = 1.1 for lignins from oat husks. The fractal analysis of the lignin macromolecules allowed us to identify the distinctive characteristics of the fractal and topological structures of these lignins. The measurements indicated that the fractal dimension (df) values of the guaiacyl-syringyl lignins from oat husks were between 1.71 and 1.85, while the df of a typical guaiacyl lignin from fir wood was ~2.3. Thus, we determined that the lignin macromolecules of oat husks belong to the diffusion-limited aggregation-type cluster–cluster class of fractals of the Meakin–Kolb type, with a predominance of characteristics common to a linear configuration. The lignins of softwood fir trees exhibited a branched topological structure, and they belong to the diffusion-limited aggregation-type particle–cluster class of fractals of the Witten–Sander type. Lignins from oat husks have the linear topology of macromolecules while the macromolecules of the lignins from fir wood can be characterized as highly branched polymers.