In a previous study, we demonstrated the feasibility of retaining poly(N-isopropylacrylamide) (pNIPAAm) on hydroxylated surfaces by spin-coating a blend of pNIPAAm with a small amount of 3-aminopropyltriethoxysilane (APTES), an organosilane, followed by thermal annealing. In this study, we detail the conditions for retaining pNIPAAm films by APTES. Our results show that the difference in surface energy between pNIPAAm and APTES in the blended film resulted in the segregation of APTES molecules to the film/substrate interface, as verified by XPS, during annealing, and the segregated APTES molecules cross-linked to form the APTES network, thus entrapping pNIPAAm. The retained pNIPAAm films (25–35 nm) exhibited thermo-responsive behavior, determined by water contact angles and film thickness in water at temperatures above and below the lower critical solution temperature of pNIPAAm, as well as good cell attachment and rapid detachment (<10 minutes). The gained insights would allow a better design of these thermo-responsive surfaces for cell sheet engineering and other relevant applications.

Silane coupling agents are commonly employed to link an organic polymer to an inorganic substrate. One of the widely utilized coupling agents is 3-aminopropyltriethoxy silane (APTES). In this study, the authors investigated the ability of APTES to retain thermo-responsive poly(N-isopropylacrylamide) (pNIPAAm) on hydroxylated surfaces such as glass. For comparison purposes, the authors also evaluated the retention behaviors of (1) polystyrene, which likely has weaker van der Waals interactions and acid-base interactions (contributed by hydrogen-bonding) with APTES, on APTES as well as (2) pNIPAAm on two other silane coupling agents, which have similar structures to APTES, but exhibit less interaction with pNIPAAm. Under our processing conditions, the stronger interactions, particularly hydrogen bonding, between pNIPAAm and APTES were found to contribute substantially to the retention of pNIPAAm on the APTES modified surface, especially on the cured APTES layer when the interpenetration was minimal or nonexistent. On the noncured APTES layer, the formation of an APTES-pNIPAAm interpenetrating network resulted in the retention of thicker pNIPAAm films. As demonstrated by water contact angles [i.e., 7 -15 higher at 40 C, the temperature above the lower critical solution temperature (LCST) of 32 C for pNIPAAm, as compared to those at 25 C] and cell attachment and detachment behaviors (i.e., attached/spread at 37 C, above LCST; detached at 20 C, below LCST), the retained pNIPAAm layer (6-15 nm), on both noncured and cured APTES, exhibited thermo-responsive behavior. The results in this study illustrate the simplicity of using the coupling/adhesion promoting ability of APTES to retain pNIPAAm films on hydroxylated substrates, which exhibit faster cell sheet detachment ( 30 min) as compared to pNIPAAm brushes (in hours) prepared using tedious and costly grafting approaches. The use of adhesion promoters to retain pNIPAAm provides an affordable alternative to current thermo-responsive supports for cell sheet engineering and stem cell therapy applications.