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Thermodynamics of N-Isopropylacrylamide in Water: Insight from Experiments, Simulations, and Kirkwood–Buff Analysis Teamwork

  • Jakub Polák
    Jakub Polák
    Department of Physical Chemistry, University of Chemistry and Technology, Prague, Technická 5, 166 28 Prague 6, Czech Republic
    More by Jakub Polák
  • Daniel Ondo*
    Daniel Ondo
    Department of Physical Chemistry, University of Chemistry and Technology, Prague, Technická 5, 166 28 Prague 6, Czech Republic
    *Email: [email protected]
    More by Daniel Ondo
  • , and 
  • Jan Heyda*
    Jan Heyda
    Department of Physical Chemistry, University of Chemistry and Technology, Prague, Technická 5, 166 28 Prague 6, Czech Republic
    *Email: [email protected]
    More by Jan Heyda
Cite this: J. Phys. Chem. B 2020, 124, 12, 2495–2504
Publication Date (Web):March 2, 2020
https://doi.org/10.1021/acs.jpcb.0c00413
Copyright © 2020 American Chemical Society

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    Abstract

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    The behavior of thermoresponsive polymer poly(N-isopropylacrylamide) (PNiPAM), an essential building block in the design of smart soft materials, in aqueous solutions has attracted much interest, which contrasts with our knowledge of N-isopropylacrylamide (NiPAM) monomer. Strikingly, the physicochemical properties of aqueous NiPAM are similarly rich, and their understanding is far from being complete. This stems from the lack of accurate thermodynamic data and quantitative model for atomistic simulations. In this joint study, we have probed the thermodynamic behavior of aqueous NiPAM by experimental methods, molecular dynamics (MD) simulations, and Kirkwood–Buff (KB) analysis at ambient conditions. From the partial molar volumes and simultaneously correlated osmotic coefficients, with excess partial molar enthalpies of NiPAM in water, the concentration and temperature dependence of KB integrals was determined. For the purpose of this work, we have developed and employed a novel NiPAM force field, which not only reproduces KB integrals (Gij) and adequately captures macroscopic thermodynamic quantities but also provides more accurate structural insight than the original force fields. We revealed in the vicinity of NiPAM the competing effect of amide hydration with interaction between nonpolar regions. This microscopic picture is reflected in the experimentally observed NiPAM–NiPAM association, which is present from highly dilute conditions up to the solubility limit and is evidenced by G22. From intermediate concentrations, it is accompanied by the existence of apparent dense-water regions, as indicated by positive G11 values. The here-employed KB-based framework provided a mutually consistent thermodynamic and microscopic insight into the NiPAM solution and may be further extended for ion-specific effects. Moreover, our findings contribute to the understanding of thermodynamic grounds behind PNiPAM collapse transition.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcb.0c00413.

    • Additional information on system compositions in MD simulations; convergence of KBI using the block averages technique; details on force-field development; optimized NiPAM force field; list of experimental data; mathematical derivation of B2 from G22; comparison of simulated and experimental data; comparison of Kirkwood–Buff integrals for aqueous amides, spatial density distribution g(r⃗) for refined force field; analysis of the formation and stability of NiPAM aggregates; and definition of gprox(r) (PDF)

    • Topology files with optimized NiPAM force field (ZIP)

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    Cited By

    This article is cited by 12 publications.

    1. Shavkat Mamatkulov, Jakub Polák, Jamoliddin Razzokov, Lukáš Tomaník, Petr Slavíček, Joachim Dzubiella, Matej Kanduč, Jan Heyda. Unveiling the Borohydride Ion through Force-Field Development. Journal of Chemical Theory and Computation 2024, 20 (3) , 1263-1273. https://doi.org/10.1021/acs.jctc.3c01020
    2. Martin Melčák, Filip Šebesta, Jan Heyda, Harry B. Gray, Stanislav Záliš, Antonín Vlček. Tryptophan to Tryptophan Hole Hopping in an Azurin Construct. The Journal of Physical Chemistry B 2024, 128 (1) , 96-108. https://doi.org/10.1021/acs.jpcb.3c06568
    3. Christine M. Papadakis, Bart-Jan Niebuur, Alfons Schulte. Thermoresponsive Polymers under Pressure with a Focus on Poly(N-isopropylacrylamide) (PNIPAM). Langmuir 2024, 40 (1) , 1-20. https://doi.org/10.1021/acs.langmuir.3c02398
    4. Stefan Hervø-Hansen, Jakub Polák, Markéta Tomandlová, Joachim Dzubiella, Jan Heyda, Mikael Lund. Salt Effects on Caffeine across Concentration Regimes. The Journal of Physical Chemistry B 2023, 127 (48) , 10253-10265. https://doi.org/10.1021/acs.jpcb.3c01085
    5. Pengcheng Huang, Rick Baldenhofer, Ricardo P. Martinho, Leon Lefferts, Jimmy A. Faria Albanese. Stimulus-Responsive Control of Transition States on Nanohybrid Polymer–Metal Catalysts. ACS Catalysis 2023, 13 (10) , 6590-6602. https://doi.org/10.1021/acscatal.3c00276
    6. Patrick K. Quoika, Maren Podewitz, Yin Wang, Anna S. Kamenik, Johannes R. Loeffler, Klaus R. Liedl. Thermosensitive Hydration of Four Acrylamide-Based Polymers in Coil and Globule Conformations. The Journal of Physical Chemistry B 2020, 124 (43) , 9745-9756. https://doi.org/10.1021/acs.jpcb.0c07232
    7. . References. 2024, 185-186. https://doi.org/10.1016/B978-0-443-21915-3.00015-3
    8. Sibasankar Panigrahy, Rahul Sahu, Sandeep K. Reddy, Divya Nayar. Structure, energetics and dynamics in crowded amino acid solutions: a molecular dynamics study. Physical Chemistry Chemical Physics 2023, 25 (7) , 5430-5442. https://doi.org/10.1039/D2CP04238J
    9. Swaminath Bharadwaj, Bart-Jan Niebuur, Katja Nothdurft, Walter Richtering, Nico F. A. van der Vegt, Christine M. Papadakis. Cononsolvency of thermoresponsive polymers: where we are now and where we are going. Soft Matter 2022, 18 (15) , 2884-2909. https://doi.org/10.1039/D2SM00146B
    10. Anna Siekierka, Katarzyna Smolińska-Kempisty, Joanna Wolska. Enhanced Specific Mechanism of Separation by Polymeric Membrane Modification—A Short Review. Membranes 2021, 11 (12) , 942. https://doi.org/10.3390/membranes11120942
    11. Kaiwen Zhang, Kun Xue, Xian Jun Loh. Thermo-Responsive Hydrogels: From Recent Progress to Biomedical Applications. Gels 2021, 7 (3) , 77. https://doi.org/10.3390/gels7030077
    12. Stanislav Záliš, Jan Heyda, Filip Šebesta, Jay R. Winkler, Harry B. Gray, Antonín Vlček. Photoinduced hole hopping through tryptophans in proteins. Proceedings of the National Academy of Sciences 2021, 118 (11) https://doi.org/10.1073/pnas.2024627118

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