Simultaneous Measurement of Mechanical and Surface Properties in Thermoresponsive, Anchored Hydrogel Films

Hydrogel films have been used extensively in the preparation of biosensors and biomedical devices. The characteristics of the aqueous interface of the polymer layer are significant for the biosensor or device function; likewise, the changing mechanical properties of thermoresponsive polymers are an important feature that affects the polymer behavior. Atomic force microscopy was used here to characterize both the surface and the mechanical properties of polymeric hydrogel films prepared from a thermoresponsive terpolymer of N-isopropylacrylamide and acrylic acid with benzophenonemethacrylate as a photoreactive cross-linker comonomer. The force–distance curves thus obtained were analyzed to assess both the surface forces and the mechanical response that were associated with the hydrogel. These properties were investigated as a function of temperature, in water and in Tris buffer, for different degrees of polymer cross-linking. For samples in water, the distance over which the surface forces were effective was found to remain constant as the temperature was increased from 26 to 42 °C, even though the mechanical response indicated that the samples had been heated past the lower critical solution temperature, or LCST. The bulk of the polymer becomes less soluble above the LCST, although this does not seem to affect the surface properties. This may be due to the segregation of the acrylic acid-rich polymer segments near the gel surface, which is in agreement with reports for related systems.