Publications

Temperature-dependent conformational changes of PNIPAM grafted chains in water : effects of molecular weight and grafting density

Kent, Michael S.; Yim, Hyun Y.

Poly(N-isopropyl acrylamide) (PNIPAM) is perhaps the most well known member of the class of responsive polymers. Free PNIPAM chains have a lower critical solution temperature in water at {approx}31 C. This very sharp transition ({approx}5 C) is attributed to alterations in the hydrogen bonding interactions of the amide group. Grafted chains of PNIPAM have shown promise for creating responsive surfaces. Examples include controlling the adsorption of proteins or bacteria, regulating the flow of liquids in narrow filaments or mesoporous materials, control of enzymatic activity, and releasing the contents of liposomes. Conformational changes of the polymer are likely to play a role in some of these applications, in addition to changes in local interactions. In this work we investigated the T-dependent conformational changes of grafted PNIPAM chains in D2O using neutron reflection and AFM. The molecular weight (M) and surface density of the PNIPAM brushes were controlled using atom-transfer radical polymerization. We discovered a strong effect of surface density. At lower surface densities, in the range typically achieved with grafting-to methods, we observed very little conformational change. At higher surface densities, significant changes with T were observed. The results will be compared with numerical SCF calculations employing an effective (conc.-dependent) Flory-Huggins chi parameter extracted from the solution phase diagram. For the case of high M and high surface density, a non-monotonic change in profile shape with T was observed. This will be discussed in the context of vertical phase separation predicted for brushes of water-soluble polymers within two-state models.