The combination of the catechol-containing comonomer dopamine methacrylamide (DMA) with stimuli-responsive poly(N-isopropylacrylamide) (PNIPAM) microgels bears a huge potential in research and for applications due to the versatile properties of catechols. This research gives the first detailed insights into the influence of DMA on the swelling of PNIPAM microgels and their nanomechanical properties. Dynamic light scattering measurements showed that DMA decreases the volume phase transition temperature and completion temperature due to its higher hydrophobicity when compared to NIPAM, while sharpening the transition. The cross-linking ability of DMA decreases the swelling ratios and mesh sizes of the microgels. Microgels adsorbed at the solid surface are characterized by atomic force microscopy─as the DMA content increases, microgels protrude more from the surface. Force spectroscopy measurements below and above the volume phase transition temperature display a stiffening of the microgels with the incorporation of DMA and upon heating across its entire cross section as evidenced by an increase in the E modulus. This confirms the cross-linking ability of DMA. The affine network factor β, derived from the Flory-Rehner theory, is linearly correlated with the E moduli of both pure PNIPAM and P(NIPAM-co-DMA) microgels. However, large DMA amounts hinder the microgel shrinking while maintaining mechanical stiffness, possibly due to catechol interactions within the microgel network.
Keywords: atomic force microscopy (AFM); catechol interactions; dynamic light scattering (DLS); mussel-inspired comonomer; nanoindentation; nanomechanical properties; stimuli-responsive microgels; swelling behavior.