PEO-PPO-PEO triblock copolymers have opposing effects
on lipid
membrane integrity: they can behave either as membrane sealants or
as membrane permeabilizers. To gain insights into their biomembrane
activities, the fundamental interactions between a series of PEO-based
polymers and phospholipid vesicles were investigated. Specifically,
the effect of copolymer hydrophobicity on its ability to prevent liposomes
from peroxidation was evaluated, and partitioning free energy and
coefficient involved in the interactions were derived. Our results
show that the high degree of hydrophilicity is a key feature of the
copolymers that can effectively protect liposomes from peroxidation
and the protective effect of the copolymers stems from their adsorption
at the membrane surface without penetrating into the bilayer core.
The origin of this protective effect induced by polymer absorption
is attributed to the retardation of membrane hydration dynamics, which
is further illustrated in the accompanying study on dynamic nuclear
polarization (DNP)-derived hydration dynamics (Cheng, C.-Y.; Wang,
J.-Y.; Kausik, R.; Lee, K. Y. C.; Han S. Biomacromolecules, 2012, DOI: 10.1021/bm300848c).