Stimuli-Responsive Langmuir Films Composed of Nanoparticles Decorated with Poly(N-isopropyl acrylamide) (PNIPAM) at the Air/Water Interface

[Image: see text] The nanotechnology shift from static toward stimuli-responsive systems is gaining momentum. We study adaptive and responsive Langmuir films at the air/water interface to facilitate the creation of two-dimensional (2D) complex systems. We verify the possibility of controlling the assembly of relatively large entities, i.e., nanoparticles with diameter around 90 nm, by inducing conformational changes within an about 5 nm poly(N-isopropyl acrylamide) (PNIPAM) capping layer. The system performs reversible switching between uniform and nonuniform states. The densely packed and uniform state is observed at a higher temperature, i.e., opposite to most phase transitions, where more ordered phases appear at lower temperatures. The induced nanoparticles’ conformational changes result in different properties of the interfacial monolayer, including various types of aggregation. The analysis of surface pressure at different temperatures and upon temperature changes, surface potential measurements, surface rheology experiments, Brewster angle microscopy (BAM), and scanning electron microscopy (SEM) observations are accompanied by calculations to discuss the principles of the nanoparticles’ self-assembly. Those findings provide guidelines for designing other adaptive 2D systems, such as programable membranes or optical interfacial devices.