Single-Chain Mechanics of Poly(N,N-diethylacrylamide) and Poly(N-isopropylacrylamide): Comparative Study Reveals the Effect of Hydrogen Bond Donors

The single-chain mechanics of two similar thermosensitive polymers, poly(N,N-diethylacrylamide) (PDEAM) and poly(N-isopropylacrylamide) (PNIPAM), have been studied by atomic force microscopy-based single-molecule force spectroscopy (SMFS). In a typical nonpolar organic solvent, octane, both of the polymers show the same inherent elasticity, although they have different substitutional groups. However, the mechanics of the two polymers presents large differences in water. The energies needed for the rearrangement of the bound water during elongation at room temperature are estimated by the SMFS method at the single-chain level, which is ~1.13 ± 0.10 and ~5.19 ± 0.10 kJ/mol for PDEAM and PNIPAM, respectively. In addition, PNIPAM shows a temperature-dependent single-chain mechanics when the temperature is increased across the lower critical solution temperature (LCST), while PDEAM does not. These differences observed in aqueous solution originate from the different structures of the two polymers. With a hydrogen bond donor in the amide group, PNIPAM will be more hydrated when T < LCST. When T > LCST, PNIPAM will have larger changes in both conformation and hydration. These findings also suggest that PNIPAM is a good candidate for a thermo-driven single-molecule motor, while PDEAM is not.