Adsorption of soft NIPAM nanogels at hydrophobic and hydrophilic interfaces: Conformation of the interfacial layers determined by neutron reflectivity.

The application of stimuli-responsive microgels and nanogels in drug delivery, catalysis, sensing, and coatings is restricted currently by the limited understanding of the factors influencing their adsorption dynamics and structural changes at interfaces. We have used neutron reflectivity to resolve, on the Ångström scale, the structure of 5% crosslinked N-isopropylacrylamide nanogels at both hydrophobic and hydrophilic interfaces in situ, as a function of temperature and bulk nanogel concentration. Our results show that the higher flexibility given by the low crosslinker content allows for a more ordered structure and packing. The adsorption of the thermoresponsive nanogels is primarily driven by temperature, more specifically its proximity to its volume phase transition temperature, while concentration plays a secondary role. Hydrophobic interactions drive the conformation of the first layer at the interface, which plays a key role in influencing the overall nanogel structure. The mobility of the first layer at the air-water interface as opposed to the interfacial confinement at the solid (SiC8)-liquid interface, results in a different conformation, a more compact and less deformed packing structure, which ultimately drives the structure of the subsequent layers. The evidence for the different structural conformations determined by the degree of hydrophobicity of the interface provides new knowledge, which is essential for the development of further applications. The key role of hydrophobic interactions in driving adsorption and interfacial behavior was also confirmed by fluid AFM experiments which visualized adherence of the nanogels to SiC8 modified surfaces.