Effect of temperature on the air-water surface mechanical behavior of water-spread block copolymer micelles

In the pursuit of the development of a first-in-kind polymer lung surfactant (PLS) therapeutic whose effects are biophysical in nature, a comprehensive understanding of the factors affecting the air-water surface mechanical behavior of water-spread block copolymer micelles is desired. To this end, we explore the effect of temperature on the surface mechanical behavior of two different micelle core chemistries, poly(styrene) (PS) and poly(tert-butyl methacrylate) (PtBMA), each having poly(ethylene glycol) (PEG) as the hydrophilic block. The behavior is characterized using surface pressure-area isotherms and quantitative Brewster angle microscopy. The results indicate that the temperature has a significant effect on the micelle structure at the interface and this effect is related to the core T_g as well as the core interfacial tension properties. When temperature is higher than the core T_g for PS-PEG, the spherical micelle core rearranges to form an oblate-like structure which increases its interfacial area. The structural rearrangement changes the mechanism by which the film produces high surface pressure. For PtBMA-PEG, which has a lower interfacial tension with water and air compared to PS, the core domains spread at the interface when the mobility is sufficiently high such that a PtBMA film is formed under high compression. The implications of these changes on PLS efficacy are discussed highlighting the importance of core T_g characterization for polymer nanoparticle applications.