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Insight into the origin of the thermosensitivity of poly[2-(dimethylamino)ethyl methacrylate].

We investigate the effects of pH and temperature on the conformational changes of poly[2-(dimethylamino)ethyl methacrylate] (PDEM) chains at the air/water interface by using Langmuir balance and sum frequency generation vibrational spectroscopy. At pH 4, the tertiary amine groups are fully charged and the PDEM chains are so hydrophilic that they completely enter into the water phase and do not exhibit thermosensitivity. At pH 7, these groups are only partially charged, and the accompanying hydration/dehydration--followed by repartitioning into the water and air phases--gives rise to a marked thermosensitivty. Finally, at pH 10, the tertiary amine groups become uncharged and thus preferentially stay in the hydrophobic air phase, devoid of associated water molecules, which results in the surface-pressure change (DeltaPi) being nearly independent of the temperature. Our Langmuir-balance experiments, coupled with surface-sensitive spectroscopy, demonstrate that: 1) the thermosensitivity of the PDEM chains relates to the hydration/dehydration of the tertiary amine groups, 2) the phase transition of thermosensitive polymers is most likely initiated by the dehydration of the chains, and 3) the phase transition of thermosensitive polymers at the air/water interface is markedly different from that in aqueous solution because of the redistribution of the macromolecular segments induced by the asymmetric forces at the air/water interface.