ACS Publications. Most Trusted. Most Cited. Most Read
Phenomena Associated with Gel–Water Interfaces. Analyses and Alternatives to the Long-Range Ordered Water Hypothesis

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. B 2013, 117, 25, 7653-7674
    Article

    Phenomena Associated with Gel–Water Interfaces. Analyses and Alternatives to the Long-Range Ordered Water Hypothesis
    Click to copy article linkArticle link copied!

    View Author Information
    Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700, United States
    *Phone: 206-543-6681. Fax: 206-685-8665. E-mail: [email protected]
    Other Access Options

    The Journal of Physical Chemistry B

    Cite this: J. Phys. Chem. B 2013, 117, 25, 7653–7674
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp302589y
    Published May 8, 2013
    Copyright © 2013 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Interfacial regions between certain gels and their surrounding solutions were observed by Pollack and co-workers to exhibit several unexpected phenomena: (1) long-range exclusion of charged microspheres out to typical distances of ∼100–200 μm from the gel surface; (2) significant electrostatic potentials extending over comparable distances; (3) a reduced intensity of upward spontaneous thermal IR emission over a region 300–500 μm wide at or near the gel–solution interface; and (4) a significantly lower proton T2 and an apparently reduced H2O self-diffusion coefficient over a zone ∼60 μm wide at or near the gel–solution interface in high resolution NMR imaging experiments. To account for such observations, they proposed that a region of long-range ordered water bearing a net negative charge, but lacking mobile charge carriers, extended ∼100–200 μm outward from the gel surface. In this paper, various problems associated with the ordered water hypothesis, including contradictions by experiments from many other laboratories, are briefly discussed, and testable alternative explanations for the observed phenomena are proposed. Exclusion zones are suggested to arise from chemotaxis of the microspheres in long-range diffusion gradients of OH– (or H+) and salt, the theory of which was developed and compared with the observations on non-ionic gels in a companion paper. The same theory together with the expected directions of ion transfers between gel and solution are now used to predict qualitatively the exclusion/attraction behavior of microspheres in the presence of ionic gels and ionomers. The electrostatic potentials are interpreted as long-range liquid-junction potentials arising from the same long-range diffusion gradients of OH– (or H+) and salt in the unstirred solutions of Pollack and co-workers. Alternative explanations in terms of plausible experimental artifacts are suggested for both the reduced intensity of IR thermal emission and the lower proton T2 and apparent H2O diffusion coefficient in the NMR imaging experiments.

    Copyright © 2013 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 27 publications.

    1. Arthur W. Snow, Ramagopal Ananth. Sulfobetaine-Siloxanes: A Class of Self-Destructive Surfactants. Langmuir 2024, 40 (9) , 4831-4844. https://doi.org/10.1021/acs.langmuir.3c03735
    2. Giulia Spatola, Alessandra Viale, Elisa Brussolo, Rita Binetti, Silvio Aime. Insights into Interfacial Water Structuring at the Nafion Surface by T1-Weighted Magnetic Resonance Imaging. Langmuir 2020, 36 (2) , 540-545. https://doi.org/10.1021/acs.langmuir.9b03435
    3. Kazuma Honma, Yukio Kimura, Yu-uta Kan-no, Shogo Tsushida, Masahito Sano. Peculiar Solvent Flow along the Gel Network after Gelation at Interfaces. The Journal of Physical Chemistry B 2018, 122 (31) , 7782-7789. https://doi.org/10.1021/acs.jpcb.8b05406
    4. Salim Ok, David W. Hoyt, Amity Andersen, Julie Sheets, Susan A. Welch, David R. Cole, Karl T. Mueller, and Nancy M. Washton . Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study. Langmuir 2017, 33 (6) , 1359-1367. https://doi.org/10.1021/acs.langmuir.6b03590
    5. J. Michael Schurr, Bryant S. Fujimoto, Leticia Huynh, and Daniel T. Chiu . A Theory of Macromolecular Chemotaxis. The Journal of Physical Chemistry B 2013, 117 (25) , 7626-7652. https://doi.org/10.1021/jp302587d
    6. G. H. Pollack. Comment on “A Theory of Macromolecular Chemotaxis” and “Phenomena Associated with Gel–Water Interfaces. Analyses and Alternatives to the Long-Range Ordered Water Hypothesis”. The Journal of Physical Chemistry B 2013, 117 (25) , 7843-7846. https://doi.org/10.1021/jp312686x
    7. Salim Ok, Julia M. Sheets, Susan A. Welch, David R. Cole. Methane–Natural Clay Interfacial Interactions as Revealed by High-Pressure Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR) Spectroscopy. Fuels 2025, 6 (1) , 16. https://doi.org/10.3390/fuels6010016
    8. I. S. Ryzhkina, L. I. Murtazina. Physicochemical patterns of dilute aqueous solutions of biologically active substances: a relationship of self-organization, properties, and bioeffects. Russian Chemical Bulletin 2024, 73 (12) , 3487-3522. https://doi.org/10.1007/s11172-024-4465-6
    9. Magdalena Kowacz, Sinith Withanage, Sebastian Niestępski. Voltage and concentration gradients across membraneless interface generated next to hydrogels: relation to glycocalyx. Soft Matter 2023, 19 (39) , 7528-7540. https://doi.org/10.1039/D3SM00889D
    10. Frauke Greil, Rajalakshmi Punampalam, Torsten H. Walther, Stefan Heißler, Anne S. Ulrich. ”Iteratively nafionated water” in its solid phase at room temperature is in fact a mixture of lyophilized biological and non-biological contaminants. Journal of Molecular Liquids 2023, 385 , 122351. https://doi.org/10.1016/j.molliq.2023.122351
    11. Sergey V. Gudkov, Maxim E. Astashev, Ilya V. Baymler, Polina N. Bolotskova, Valery A. Kozlov, Alexander V. Simakin, Minh T. Khuong, Polina A. Fomina, Nikolai F. Bunkin. Effects of Low-Frequency Randomly Polarized Electromagnetic Radiation, as Revealed upon Swelling of Polymer Membrane in Water with Different Isotopic Compositions. Materials 2023, 16 (13) , 4622. https://doi.org/10.3390/ma16134622
    12. D. B. Kuznetsov, A. Yu. Mironov, V. A. Neschislyaev, I. L. Volkhin, E. V. Orlova, A. D. Shilina. Restoration of the Indicator Properties of Whole-cell Luminescent Biosensors. Applied Biochemistry and Biotechnology 2022, 194 (9) , 4081-4092. https://doi.org/10.1007/s12010-022-03977-7
    13. A Earls, M-C Calderer, M Desroches, A Zarnescu, S Rodrigues. A phenomenological model for interfacial water near hydrophilic polymers. Journal of Physics: Condensed Matter 2022, 34 (35) , 355102. https://doi.org/10.1088/1361-648X/ac7b5d
    14. Georgios M. Kontogeorgis, Andrew Holster, Nomiki Kottaki, Evangelos Tsochantaris, Frederik Topsøe, Jesper Poulsen, Michael Bache, Xiaodong Liang, Nikolaj Sorgenfrei Blom, Johan Kronholm. Water structure, properties and some applications – A review. Chemical Thermodynamics and Thermal Analysis 2022, 6 , 100053. https://doi.org/10.1016/j.ctta.2022.100053
    15. Yujuan Hu, Ying Zhang, Yangjian Cheng. Kinetic insight on the long-range exclusion of dissolved substances by interfacial interactions of water and hydrophilic surface. Journal of Molecular Liquids 2022, 349 , 118118. https://doi.org/10.1016/j.molliq.2021.118118
    16. H. Mercado-Uribe, F. J. Guevara-Pantoja, W. García-Muñoz, J. S. García-Maldonado, J. M. Méndez-Alcaraz, J. C. Ruiz-Suárez. On the evolution of the exclusion zone produced by hydrophilic surfaces: A contracted description. The Journal of Chemical Physics 2021, 154 (19) https://doi.org/10.1063/5.0043084
    17. Daniel C. Elton, Peter D. Spencer. Pathological Water Science – Four Examples and What They Have in Common. 2021, 155-169. https://doi.org/10.1007/978-3-030-67227-0_8
    18. Barry W. Ninham, Polina N. Bolotskova, Sergey V. Gudkov, Yulchi Juraev, Mariya S. Kiryanova, Valeriy A. Kozlov, Roman S. Safronenkov, Alexey V. Shkirin, Elena V. Uspenskaya, Nikolai F. Bunkin. Formation of Water-Free Cavity in the Process of Nafion Swelling in a Cell of Limited Volume; Effect of Polymer Fibers Unwinding. Polymers 2020, 12 (12) , 2888. https://doi.org/10.3390/polym12122888
    19. Daniel C. Elton, Peter D. Spencer, James D. Riches, Elizabeth D. Williams. Exclusion Zone Phenomena in Water—A Critical Review of Experimental Findings and Theories. International Journal of Molecular Sciences 2020, 21 (14) , 5041. https://doi.org/10.3390/ijms21145041
    20. Zheng Li, Gerald H. Pollack. Surface-induced flow: A natural microscopic engine using infrared energy as fuel. Science Advances 2020, 6 (19) https://doi.org/10.1126/sciadv.aba0941
    21. Maria J. Esplandiu, David Reguera, Jordi Fraxedas. Electrophoretic origin of long-range repulsion of colloids near water/Nafion interfaces. Soft Matter 2020, 16 (15) , 3717-3726. https://doi.org/10.1039/D0SM00170H
    22. Peter D. Spencer, James D. Riches, Elizabeth D. Williams. Exclusion zone water is associated with material that exhibits proton diffusion but not birefringent properties. Fluid Phase Equilibria 2018, 466 , 103-109. https://doi.org/10.1016/j.fluid.2018.03.020
    23. Laurent Jaeken. The neglected functions of intrinsically disordered proteins and the origin of life. Progress in Biophysics and Molecular Biology 2017, 126 , 31-46. https://doi.org/10.1016/j.pbiomolbio.2017.03.002
    24. Sami Musa, Daniel Florea, Hans M. Wyss, Jacques M. Huyghe. Convection associated with exclusion zone formation in colloidal suspensions. Soft Matter 2016, 12 (4) , 1127-1132. https://doi.org/10.1039/C5SM01502B
    25. N. F. Bunkin, V. A. Kozlov, I. N. Aliev, I. I. Molchanov, S. A. Abdullaev, K. N. Belosludtsev, M. E. Astashev, S. V. Gudkov. Investigation of the phase states of aqueous salt solutions near a polymer membrane surface. Physics of Wave Phenomena 2015, 23 (4) , 255-264. https://doi.org/10.3103/S1541308X15040020
    26. István Huszár, Zsolt Mártonfalvi, András Laki, Kristóf Iván, Miklós Kellermayer. Exclusion-Zone Dynamics Explored with Microfluidics and Optical Tweezers. Entropy 2014, 16 (8) , 4322-4337. https://doi.org/10.3390/e16084322
    27. Daniel Florea, Sami Musa, Jacques M. R. Huyghe, Hans M. Wyss. Long-range repulsion of colloids driven by ion exchange and diffusiophoresis. Proceedings of the National Academy of Sciences 2014, 111 (18) , 6554-6559. https://doi.org/10.1073/pnas.1322857111
    Download PDF
    Go to The Journal of Physical Chemistry B
    Get e-Alerts
    Get e-Alerts

    The Journal of Physical Chemistry B

    Cite this: J. Phys. Chem. B 2013, 117, 25, 7653–7674
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp302589y
    Published May 8, 2013
    Copyright © 2013 American Chemical Society
    Request reuse permissions

    Article Views

    783

    Altmetric

    -

    Citations

    27
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.