Plasticity or elasticity? Relating elastic moduli with secondary structural features of mixed films of polypeptides at air/fluid and fluid/solid interfaces

Abstract

Viscoelastic properties of molecular assemblies formed by mixing poly (l-lysine) (PLL) and poly (l-glutamic acid) (PGA) at pH = 7.5 have been studied using Quartz crystal microbalance with dissipation (QCM-D). The inter-molecular complex between PLL and PGA arising from strong electrostatic interaction, leads to local changes in secondary structure resulting in intra-molecular complexes. ATR-FTIR analysis of the Secondary structural features of PLL, suggest an abundance of anti-parallel beta sheet that causes a significant change in the morphology of the self-assembled structures. A combination of spectroscopy, Brewster angle microscopy (BAM), Transmission electron and scanning electron microscopy show that an inverse relationship exists between the elasticity of the different PLL + PGA mixed films and the % anti parallel beta sheet conformation. The elastic moduli for the mixtures change from about 0.913 ± 0.01 GPa for pure PLL to about 0.764 ± 0.01 GPa in the mixture when PGA increases. The localized breaking and reformation of the ion pairs in the complex control their sizes and show an inverse relationship with the elastic moduli. The rheological profiles of the films, elastic moduli, together with their surface morphology from microscopy (TEM) and (SEM) confirmed their increasing propensity to self-assemble in one dimension to form tapes, colloidal particles and their composite assemblies.