Abstract
The behaviour of water in nanopores is very different from that of bulk water1,2. Close to hydrophobic surfaces, the water density has been found to be lower than in the bulk3, and if confined in a sufficiently narrow hydrophobic nanopore, water can spontaneously evaporate1,4. Molecular dynamics simulations have suggested that a nanopore can be switched between dry and wet states by applying an electric potential across the nanopore membrane5,6,7,8. Nanopores with hydrophobic walls could therefore create a gate system for water, and also for ionic and neutral species. Here, we show that single hydrophobic nanopores can undergo reversible wetting and dewetting due to condensation and evaporation of water inside the pores. The reversible process is observed as fluctuations between conducting and non-conducting ionic states and can be regulated by a transmembrane electric potential.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Israelachvili, J. N. Intermolecular and Surface Forces (Academic Press, 1991).
Meyer, E. E., Rosenberg, K. J. & Israelachvili, J. Recent progress in understanding hydrophobic interactions. Proc. Natl Acad. Sci. USA 103, 15739–15746 (2006).
Doshi, D. A., Watkins, E. B., Israelachvili, J. & Majewski, J. Reduced water density at hydrophobic surfaces: effect of dissolved gases. Proc. Natl Acad. Sci. USA 102, 9458–9462 (2005).
Lum, K., Chandler, D. & Weeks, J. D. Hydrophobicity at small and large length scales. J. Phys. Chem. B 103, 4570–4577 (1999).
Vaitheeswaran, S., Rasaiah, J. C. & Hummer, G. Electric field and temperature effects on water in the narrow nonpolar pores of carbon nanotubes. J. Chem. Phys. 121, 7955–7965 (2004).
Dzubiella, J., Allen, R. J. & Hansen, J.-P. Electric field-controlled water permeation coupled to ion transport through a nanopore. J. Chem. Phys. 120, 5001–5004 (2004).
Dzubiella, J. & Hansen, J.-P. Electric-field-controlled water and ion permeation of a hydrophobic nanopore. J. Chem. Phys. 122, 234706 (2005).
Bratko, D., Daub, C. D., Leung, K. & Luzar, A. Effect of field direction on electrowetting in a nanopore. J. Am. Chem. Soc. 129, 2504–2510 (2007).
Smirnov, S., Vlassiouk, I., Takmakov, P. & Rios, F. Water confinement in hydrophobic nanopores. Pressure-induced wetting and drying. ACS Nano 4, 5069–5075 (2010).
Smirnov, S. N., Vlassiouk, I. V. & Lavrik, N. V. Voltage-gated hydrophobic nanopores. ACS Nano 5, 7453–7461 (2011).
Sukharev, S. I., Sigurdson, W. J., Kung, C. & Sachs, F. Energetic and spatial parameters for gating of the bacterial large conductance mechanosensitive channel, MscL. J. Gen. Physiol. 113, 525–540 (1999).
Jensen, M. Ø. et al. Principles of conduction and hydrophobic gating in K+ channels. Proc. Natl Acad. Sci. USA 107, 5833–5838 (2010).
Roth, R., Gillespie, D., Nonner, W. & Eisenberg, R. E. Bubbles, gating, and anesthetics in ion channels. Biophys. J. 94, 4282–4298 (2008).
Vlassiouk, I., Park, C-D., Vail, S. A., Gust, D. & Smirnov, S. Control of nanopore wetting by a photochromic spiropyran: a light-controlled valve and electrical switch. Nano Lett. 6, 1013–1017 (2006).
Leung, K., Luzar, A. & Bratko, D. Dynamics of capillary drying in water. Phys. Rev. Lett. 90, 065502 (2003).
Hummer, G., Rasaiah, J. C. & Noworyta, J. P. Water conduction through the hydrophobic channel of a carbon nanotube. Nature 414, 188–190 (2001).
Beckstein, O. & Sansom, M. S. P. Liquid-vapor oscillations of water in hydrophobic nanopores. Proc. Natl Acad. Sci. USA 100, 7063–7068 (2003).
Fleischer, R. L., Price, P. B. & Walker, R. M. Nuclear Tracks in Solids. Principles and Applications (Univ. California Press, 1975).
Apel, A., Korchev, Y. E., Siwy, Z., Spohr, R. & Yoshida, M. Diode-like single-ion track membrane prepared by electro-stopping. Nucl. Instrum. Methods Phys. Res. B 184, 337–346 (2001).
Siwy, Z. & Fulinski, A. Fabrication of a synthetic nanopore ion-pump. Phys. Rev. Lett. 89, 198103 (2002).
Siwy, Z. S. & Howorka, S. Engineered voltage-responsive nanopores. Chem. Soc. Rev. 39, 1115–1132 (2010).
Shirono, K., Tatsumi, N. & Daiguji, H. Molecular simulation of ion transport in silica nanopores. J. Phys. Chem. B 113, 1041–1047 (2009).
Beckstein, O., Tai, K. & Sansom, M. S. P. Not ions alone: barriers to ion permeation in nanopores and channels. J. Am. Chem. Soc. 126, 14694–14695 (2004).
Tajkhorshid, E. et al. Control of the selectivity of the aquaporin water channel family by global orientational tuning. Science 296, 525–530 (2002).
Giovambattista, N., Debenedetti, P. G. & Rossky, P. J. Hydration behavior under confinement by nanoscale surfaces with patterned hydrophobicity and hydrophilicity. J. Phys. Chem. C 111, 1323–1332 (2007).
Parikesit, G. O. F., Vrouwe, E. X., Blom, M. T. & Westerweel, J. Observation of hydrophobic-like behavior in geometrically patterned hydrophilic microchannels. Biomicrofluidics 4, 044103 (2010).
Koishi, T., Yasuoka, K., Ebisuzaki, T., Yoo, S. & Zeng, X. C. Large-scale molecular-dynamics simulation of nanoscale hydrophobic interaction and nanobubble formation. J. Chem. Phys. 123, 204707 (2005).
Acknowledgements
Irradiation with swift heavy ions was performed at the Gesellschaft fuer Schwerionenforschung (GSI, Darmstadt, Germany). This research was supported by the National Science Foundation (CHE 0747237). Z.S.S. was supported as part of the Nanostructures for Electrical Energy Storage, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (award no. DESC0001160). The authors acknowledge discussions with C. Martens.
Author information
Authors and Affiliations
Contributions
Z.S.S., M.D. and K.J.S. conceived the experiments. M.R.P., L.C. and M.D. performed the experiments. All authors contributed to writing the manuscript. M.R.P., L.C., M.D., K.J.S. and Z.S.S. discussed the results and explained the transient behaviour of ion current in hydrophobic pores.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary information
Supplementary information (PDF 1323 kb)
Rights and permissions
About this article
Cite this article
Powell, M., Cleary, L., Davenport, M. et al. Electric-field-induced wetting and dewetting in single hydrophobic nanopores. Nature Nanotech 6, 798–802 (2011). https://doi.org/10.1038/nnano.2011.189
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nnano.2011.189
This article is cited by
-
Hydrophobically gated memristive nanopores for neuromorphic applications
Nature Communications (2023)
-
Flexibly designable wettability gradient for passive control of fluid motion via physical surface modification
Scientific Reports (2023)
-
Pressure-sensitive conversions between Cassie and Wenzel wetting states on a nanocorrugated surface
Applied Physics A (2022)
-
Evaporation-driven transport-control of small molecules along nanoslits
Nature Communications (2021)
-
Interactive effect of pH and cation valence in background electrolyte solutions on simazine sorption to Miscanthus biochar produced at two different pyrolysis temperatures
Korean Journal of Chemical Engineering (2020)