Poly(N-isopropylacrylamide)-Based Mixed Brushes: A Computer Simulation Study.

Abstract

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPAM) polymer brushes of fixed molecular weight and grafting density are modeled in the framework of a coarse-grained model with soft, nonbonded interactions and an implicit solvent. This model has been developed to address experimentally relevant, large invariant degrees of polymerization, and nonbonded interactions are expressed via a third-order (virial) expansion of the equation of state. The choice of interaction parameters is intended to mimic the swelling behavior of PNIPAM in water as the temperature increases toward the lower critical solution temperature (T(LCST)). Results of molecular dynamics simulations for one component brushes are compared to experimental data. Mixed brushes incorporating small and large amounts of grafted poly(ethylene glycol) polymers are then considered. The effects of mixing polymer components on the response of the mixed brushes to temperature changes are monitored, and the results are compared to experimental data. In the end, two design principles for biomolecule triggering using temperature-sensitive mixed polymer brushes with functional and switchable end-groups are proposed and studied. This work is in favor of establishing qualitative rules for the design, optimization, and comprehension of binary polymer brushes for bioengineering purposes.