Influence of ionic strength on poly(diallyldimethylammonium chloride) macromolecule conformations in electrolyte...

Conformations of poly(diallyldimethylammonium chloride), PDADMAC, molecules in electrolyte solutions were experimentally evaluated by dynamic light scattering (DLS), micro-electrophoretic and viscosity measurements. The role of ionic strength varied within 10(-4) and 2M was systematically studied. The diffusion coefficient of the polymer molecules was equal to 1.3×10(-7)cm(2)s(-1) for the ionic strength range 5×10(-4) to 10(-2)M decreasing slightly for higher ionic strength. This corresponds to the hydrodynamic diameter of 38.5nm. Using the diffusion coefficient and the electrophoretic mobility data, the electrokinetic charge on PDADMAC molecules was calculated as a function of ionic strength. It was positive and varied between 84 and 51 elementary charges. This gives the effective ionization degree of the macromolecule equal to 13% and 8% for ionic strength of 5×10(-4) and 0.15M, respectively. Additional information about macromolecule conformation was derived from the viscosity measurements of dilute PDADMAC solutions. The intrinsic viscosity derived from these measurements decreased abruptly with ionic strength from 3400 for 10(-4)M to 100 for 2M, NaCl solutions. By extrapolating the hydrodynamic diameter and intrinsic viscosity data to zero ionic strength the polyelectrolyte molecule contour length of 240nm and the backbone diameter of 0.85nm were predicted. On the other hand, the decrease in the intrinsic viscosity for higher ionic strength was attributed to changes in macromolecule conformations to more collapsed ones. The experimental results were interpreted by molecular dynamics modeling of PDADMAC chain conformations in electrolyte solutions where the ionic strength effect and the effective ionization degree were considered. A quantitative agreement was attained for lower ionic strength range proving that the combined DLS and viscosity measurements furnish reliable information about macromolecule conformations in electrolyte solution.