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• W4294844975 startingPage "7066" @default.
• W4294844975 abstract "Poly-N-isopropylacrylamide (PNIPAM) is a thermo-responsive polymer that exhibits a reversible structural change from extended chains to aggregates in aqueous solution above its lower critical solution temperature (LCST). Using polarization-selective IR pump-probe spectroscopy, the water orientational dynamics in PNIPAM from below to above the LCST were examined and compared to those of its monomer solution, N-isopropylacrylamide (NIPAM), polyacrylamide, and an acrylamide monomer solution, which are not thermo-responsive. The OD stretch of dilute HOD in H2O is used as a vibrational probe of water orientational dynamics. Below the LCST of the polymer, NIPAM and PNIPAM solutions exhibited identical water dynamics that were significantly different from those of bulk water, containing both faster and slower components due to solute-water interactions. Therefore, there is no difference in the nature of water interactions with a single NIPAM moiety and a long polymer chain. For all systems, including PNIPAM below and above the LCST, the orientational dynamics were modeled with a bulk water component and a polymer/monomer-associated component based on previous experimental and computational findings. Above the LCST, PNIPAM showed fast water orientational relaxation but much slower long-time dynamics compared to those of NIPAM. The slow component in PNIPAM, which was too slow to be accurately measured due to the limited OD vibrational lifetime, is ascribed to water confined in small voids (<2 nm in diameter) of PNIPAM globules. These results highlight important details about thermo-responsive polymers and the dynamics of their solvation water as they undergo a significant structural change." @default.
• W4294844975 created "2022-09-07" @default.
• W4294844975 creator A5046798803 @default.
• W4294844975 creator A5066606307 @default.
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• W4294844975 date "2022-09-06" @default.
• W4294844975 modified "2023-09-26" @default.
• W4294844975 title "Water Dynamics in Aqueous Poly-<i>N</i>-Isopropylacrylamide Below and Through the Lower Critical Solution Temperature" @default.
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• W4294844975 doi "https://doi.org/10.1021/acs.jpcb.2c05506" @default.
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