Thermodynamics of micellization of β-sheet forming poly(acrylic acid)-block-poly(l-valine) hybrids

The phase behavior and thermodynamic of micellization of three hybrid poly(acrylic acid)-block-poly(l-valine), namely PAA(40)-b-PLVAL(100), PAA(80)-b-PLVAL(100), and PAA(80)-b-PLVAL(80), were investigated. beta-sheet formation in these polymeric systems resulted in a dominant enthalpic micellization process that exhibited an upper critical solution temperature (UCST). Micelle dissociation at higher temperatures is attributed to the disruption of favorable hydrogen bonds in the micellar core. Separation of hydrogen bond contributions to the micellization thermodynamics through the addition of urea as an external denaturing agent, revealed a shift from a dominant enthalpic contribution of PLVAL segments at low degree of deprotonation (alpha), where significant beta-sheet is formed, to a balanced enthalpy and entropy contributions at high alpha, At high alpha, an enhanced water cage hydration of unimers was observed due to the formation of water-PLVAL hydrogen bonds. Hydrophobic forces played an indirect role in enhancing the compactness of the hydrophobic core, which enhanced the strength of hydrogen bonds in the beta-sheet structures.