Polyzwitterion fast and slow mode behavior are coupled to phase separation as observed by dynamic laser light...

A model zwitterionic polysulfobetaine, poly(3-(acrylamidopropyl-dimethyl-ammonium) propyl-1-sulfonate) (pAPAPS), phase separates upon cooling and exhibits an upper critical solution temperature (UCST) behavior with no added salt in deuterium oxide solutions. Dynamic light scattering measurements indicate the presence of distinct fast and slow diffusive modes, where the fast mode is interpreted as a collective diffusion coefficient and the slow mode is attributed to the diffusion of multi-chain dynamic clusters. The relative population of fast and slow modes varies systematically with temperature and concentration. A clustering temperature (T*) was assigned when the slow mode first appeared upon cooling. The slow mode then increases in relative scattering amplitude as the phase boundary is approached. The fast mode exhibits a concentration dependence above T* consistent with the virial expansion in the collective diffusion. The sign of the virial coefficient (kd) is negative, even in the good solvent region above the expected Flory temperature (Θ ≈ 39 °C), a behavior distinct from synthetic neutral polymers in organic solvents. The onset of multi-chain clustering at T < T* coincides with the poor solvent regime (T < Θ). Attractive dipolar interactions due to the zwitterionic sulfobetaine groups in pAPAPS are suggested as the origin of the multi-chain clusters with no salt. Upon the addition of 100 mM NaCl, the slow mode is suppressed, and the hydrodynamic radius is consistent with polyzwitterion chain dimensions in a dilute solution. We find that concentration dependent diffusion is highly linked to the theta temperature and the emergence of dynamic clusters as the polymer goes from good to poor solvent on approach to the UCST. The slow mode in the semidilute regime is reported along with preliminary small-angle neutron scattering data that show salt reduces clustering and leads to predominantly chain scattering.