Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Electric-field-induced wetting and dewetting in single hydrophobic nanopores

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

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

Figure 1: Hydrophobic gating in a 16-nm-diameter conically shaped nanopore modified in 12 mM (trimethylsilyl)diazomethane for 15 min.
Figure 2: Reversibility of the opening and closing of a hydrophobic nanopore with voltage.
Figure 3: Hydrophobic gating studied in a degassed solution of 1 M KCl.
Figure 4: Scheme of hydrophobic gating with an electric field.

Similar content being viewed by others

References

  1. Israelachvili, J. N. Intermolecular and Surface Forces (Academic Press, 1991).

    Google Scholar 

  2. Meyer, E. E., Rosenberg, K. J. & Israelachvili, J. Recent progress in understanding hydrophobic interactions. Proc. Natl Acad. Sci. USA 103, 15739–15746 (2006).

    Article  CAS  Google Scholar 

  3. 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).

    Article  CAS  Google Scholar 

  4. Lum, K., Chandler, D. & Weeks, J. D. Hydrophobicity at small and large length scales. J. Phys. Chem. B 103, 4570–4577 (1999).

    Article  CAS  Google Scholar 

  5. 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).

    Article  CAS  Google Scholar 

  6. 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).

    Article  CAS  Google Scholar 

  7. Dzubiella, J. & Hansen, J.-P. Electric-field-controlled water and ion permeation of a hydrophobic nanopore. J. Chem. Phys. 122, 234706 (2005).

    Article  CAS  Google Scholar 

  8. 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).

    Article  CAS  Google Scholar 

  9. Smirnov, S., Vlassiouk, I., Takmakov, P. & Rios, F. Water confinement in hydrophobic nanopores. Pressure-induced wetting and drying. ACS Nano 4, 5069–5075 (2010).

    Article  CAS  Google Scholar 

  10. Smirnov, S. N., Vlassiouk, I. V. & Lavrik, N. V. Voltage-gated hydrophobic nanopores. ACS Nano 5, 7453–7461 (2011).

    Article  CAS  Google Scholar 

  11. 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).

    Article  CAS  Google Scholar 

  12. Jensen, M. Ø. et al. Principles of conduction and hydrophobic gating in K+ channels. Proc. Natl Acad. Sci. USA 107, 5833–5838 (2010).

    Article  CAS  Google Scholar 

  13. Roth, R., Gillespie, D., Nonner, W. & Eisenberg, R. E. Bubbles, gating, and anesthetics in ion channels. Biophys. J. 94, 4282–4298 (2008).

    Article  CAS  Google Scholar 

  14. 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).

    Article  CAS  Google Scholar 

  15. Leung, K., Luzar, A. & Bratko, D. Dynamics of capillary drying in water. Phys. Rev. Lett. 90, 065502 (2003).

    Article  Google Scholar 

  16. Hummer, G., Rasaiah, J. C. & Noworyta, J. P. Water conduction through the hydrophobic channel of a carbon nanotube. Nature 414, 188–190 (2001).

    Article  CAS  Google Scholar 

  17. Beckstein, O. & Sansom, M. S. P. Liquid-vapor oscillations of water in hydrophobic nanopores. Proc. Natl Acad. Sci. USA 100, 7063–7068 (2003).

    Article  CAS  Google Scholar 

  18. Fleischer, R. L., Price, P. B. & Walker, R. M. Nuclear Tracks in Solids. Principles and Applications (Univ. California Press, 1975).

    Google Scholar 

  19. 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).

    Article  CAS  Google Scholar 

  20. Siwy, Z. & Fulinski, A. Fabrication of a synthetic nanopore ion-pump. Phys. Rev. Lett. 89, 198103 (2002).

    Article  CAS  Google Scholar 

  21. Siwy, Z. S. & Howorka, S. Engineered voltage-responsive nanopores. Chem. Soc. Rev. 39, 1115–1132 (2010).

    Article  CAS  Google Scholar 

  22. Shirono, K., Tatsumi, N. & Daiguji, H. Molecular simulation of ion transport in silica nanopores. J. Phys. Chem. B 113, 1041–1047 (2009).

    Article  CAS  Google Scholar 

  23. 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).

    Article  CAS  Google Scholar 

  24. Tajkhorshid, E. et al. Control of the selectivity of the aquaporin water channel family by global orientational tuning. Science 296, 525–530 (2002).

    Article  CAS  Google Scholar 

  25. 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).

    Article  CAS  Google Scholar 

  26. 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).

    Article  CAS  Google Scholar 

  27. 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).

    Article  Google Scholar 

Download references

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

Authors

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

Correspondence to Zuzanna S. Siwy.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 1323 kb)

Rights and permissions

Reprints 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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nnano.2011.189

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing