Summary
High-density ZnO nanorods of 60–80 nm in diameter and 500–700 nm in length grown on the silver-coated tip of a borosilicate glass capillary (0.7 μm in diameter) demonstrate a remarkable linear response to proton H3O+ concentrations in solution. These nanorods were used to create a highly sensitive pH sensor for monitoring in vivo biological process within single cells. The ZnO nanorods exhibit a pH-dependent electrochemical potential difference versus an Ag/AgCl microelectrode. The potential difference was linear over a large dynamic range (pH, 4–11) and had a sensitivity equal to 51.88 mV/pH at 22°C, which could be understood in terms of changes in surface charge during protonation and deprotonation. Vertically grown nanoelectrodes of this type can be smoothly and gently applied to penetrate a single living cell without causing cell apoptosis.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Similar content being viewed by others
References
Zheng, G., Patolsky, F., Cui, Y., Wang, W. U., and Lieber, C. M. (2005). Multiplexed electrical detection of cancer markers with nanowire sensor arrays. Nature Biotechnology 23, 1294–1301
Cui, Y., Wei, Q., Park, H., Lieber, C. M. (2001). Nanowire nanosensors for highly sensitive and selective detection of biological and chemical species. Science 293, 1289–1292
Popovtzer, R., Neufeld, T., Ron, E. Z., Rishpon, J., and Shacham-Diamand, Y. (2006). Electrochemical detection of biological reactions using a novel nano-bio-chip array. Sensors and Actuators B 119, 664–672
Cai, X., Klauke, N., Glidle, A., Cobbold, P., Smith G. L., and Cooper, J. M. (2002). Ultra-low-volume, real-time measurements of lactate from the single heart cell using microsystems technology. Analytical Chemistry 74, 908–914
Zwicker, G. and Jacobi, K. (1983). Site-specific interaction of H2O with ZnO single-crystal surfaces studied by thermal desorption and UV photoelectron spectroscopy. Surface Science 131, 179–194
Parker, T. M., Condon, N. G., Lindsay, R., Leibsle, F.M., and Thornton, G. (1998). Imaging the polar (0001–ī) and non-polar (101–ī0) surfaces of ZnO with STM. Surface Science 415, L1046–L1050
Matsunaga, K., Oba, F., Tanaka, I., and Adachi, H. (1999). Valence band structure of ZnO (1010) surface by cluster calculation. Journal of Electroceramics 4, 69–80
Wander, A. and Harrison, N. M. (2001). The stability of polar oxide surfaces: The interaction of H2O with ZnO (0001) and ZnO(0001–ī). Journal of Chemical Physics 115, 2312–2316
Wander, A., Schedin, F., Steadman, P., Norris, A., McGrath, R., Turner, T.S., Thornton, G., and Harrison, N. M. (2001). Stability of polar oxide surfaces. Physical Review Letters 86, 3811–3814
Dulub, O., Boatner, L. A., and Diebold, U. (2002). STM study of the geometric and electronic structure of ZnO (0001)-Zn, (0001–ī)-o,(101–ī0), and (11\2–ī0) surfaces. Surface Science 519, 201–207
Kresse, G., Dulub, O., and Diebold, U. (2003). Competing stabilization mechanism for the polar ZnO(0001)-Zn surface. Physical Review B 68, 245409–(15 pages)
Dulub, O., Diebold, U., and Kresse, G. (2003). Novel stabilization mechanism on polar surfaces: Zn(0001)-Zn. Physical Review Letters 90, 016102–(4 pages)
Meyer, B., Marx, D., and Dulub, O. (2004). Partial dissociation of water leads to stable superstructures on the surface of zinc oxide. Angewandte Chemie (International ed. in English) 43, 6642–6645
Meyer, B. (2004). First principles study of the polar O-terminated ZnO surface in thermodynamic equilibrium with oxygen and hydrogen. Physical Review B 69, 045416–(10 pages)
Dulub, O., Meyer, B., and Diebold, U. (2005). Observation of the dynamical in a water monolayer adsorbed on a ZnO surface. Physical Review Letters 95, 136101–(4 pages)
Glab, S., Hulanicki, A., Edwall, G., and Ingman, F. (1989) Metal-metal oxide and metal oxide electrodes as pH sensors. Analytical Chemistry 21, 29–46
Cammann, K., Ross, B., Katerkamp, A., Reinbold, J., Grundig, R., and Renneberg, R. (2002). Chemical and Biochemical Sensors. Wiley-VCH verlag GmbH & Co. KGaA, Ullmann’s encyclopedia of industrial chemistry
Wang, H., Nakamura, H., Yao, K., Uehara, M., Nishimura, S., Maeda, H., and Abe, E. (2002). Effect of polyelectrolyte dispersants on the preparation of silica-coated zinc oxide particles in aqueous media. Journal of the American Ceramic Society 85, 1937–1940
Caldwell, P. C. (1954). An investigation of the intracellular pH of crab muscle fibres by means of micro-glass and micro-tungsten electrode. Journal of Physiology 126, 169–180
Thomas, R. C. (1974). Intracellular pH of snail neurons measured with a new pH-sensitive glass micro-electrode. Journal of Physiology 238, 159–180
Yan, Y. and Al-Jassim, M. M. (2005). Structure and energetics of water adsorbed on the ZnO(101–ī0) surface. Physical Review B 72, 235406–(6 pages)
Martins, J. B. L., Longo, E., Salmon, O. D. R., Espinoza, V. A. A., and Taft, C. A. (2004).w The interaction of H2, CO, CO2, H2O and NH3 on ZnO surfaces: an Oniom study. Chemical Physics Letters 400, 481–486
Martins, J. B. L., Andres, J., Longo, E., and Taft, C. A. (1996). Properties, dynamics, and electronic structure of condensed systems H2O and H2 interaction with ZnO surfaces: A MNDO, AM1, and PM3 theoretical study with large cluster models. International Journal of Quantum Chemistry 57, 861–870
Martins, J. B. L., Moliner, V., Andres, J., Longo, E., and Taft, C. A. (1995). A theoretical study of water adsorption on (101–ī0) and (0001) ZnO surfaces: molecular cluster, basis set and effective core potential dependence. Journal of Molecular Structure (Theochem) 330, 347–351
Stumm, W. and Morgan, J. J. (1981). Precipitation and dissolution. In: Aquatic Chemistry: An Introduction Emphasizing Chemical Equilibria in Natural Waters. (John Wiley&Sons), New York, pp. 230–322
Al-Hilli, S., Öst, A., and Strålfors, P., and Willander, M. (2007). ZnO nanorods as an intracellular sensor for pH measurements. Journal of Applied Physics 102, 084304–(5 pages)
Greene, L. E., Law, M., Goldberger, J., Kim, F., Johnson, J. C., Zhang, Y., Saykally, R. J., and Yang, P. (2003). Low-temperature wafer-scale production of ZnO nanowire arrays. Angewandte Chemie (International ed. in English) 42, 3031–3034
Vayssieres, L., Keis, K., Lindquist, S., and Hagfeldt, A. (2001). Purpose-built anisotropic metal oxide material: 3D highly oriented microrod array of ZnO. The Journal of Physical Chemistry B 105, 3350–3352
Li, Q., Kumar, V., Li, Y., Zhang, H., Marks, T. J., and Chang, R. P. H. (2005). Fabrication of ZnO nanorods and nanotubes in aqueous solutions. Chemistry of Materials 17, 1001–1006
Zhou, J., Xu, N., and Wang, Z. L. (2006). Dissolving behavior and stability of ZnO wires in biofluids: a study on biodegradability and biocompatibility of ZnO nanostructures. Advanced Materials 18, 2432–2435
Lee, S. C., Hamilton, J. S., Trammell, T., Horwitz, B., and Pappone, P. A. (1994). Adrenergic modulation of intracellular pH in isolated brown fat cells from hamster and rat. American Journal of Physiology Cell Physiology 267, C349–C356
Shrode, L. D., Tapper, H., and Grinstein, S. (1997). Role of intracellular pH in proliferation, transformation, and apoptosis. Journal of Bioenergetics and Biomembranes 29, 393–399
Strålfors, P. and Honno, R. C. (1989). Insulin-induced dephosphorylation of hormone-sensitive lipase-correlation with lipolysis and cAMP-dependent protein kinase activity. European Journal of Biochemistry 182, 379–385
Danielsson, A., Öst, A., Lystedt, E., Kjolhede, P., Gustavsson, J., Nystrom, F. H., and Strålfors, P. (2005). Insulin resistance in human adipocytes occurs downstream of IRS1 after surgical cell isolation but at the level of phosphorylation of IRS1 in type 2 diabetes. FEBS Journal 272, 141–151
Pollock, A.S. (1984). Intracellular pH of hepatocytes in primary monolayer culture. American Journal of Physiology. Renal Physiology 246, F738–F744
Acknowledgments
The authors gratefully acknowledge the financial support from the Swedish Research Council and Molecular Skin Research Platform within the Faculty of Science at Göteborg University.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2009 Humana Press, a part of Springer Science+Business Media, LLC
About this protocol
Cite this protocol
Willander, M., Al-Hilli, S. (2009). ZnO Nanorods as an Intracellular Sensor for pH Measurements. In: Foote, R., Lee, J. (eds) Micro and Nano Technologies in Bioanalysis. Methods in Molecular Biology™, vol 544. Humana Press, Totowa, NJ. https://doi.org/10.1007/978-1-59745-483-4_13
Download citation
DOI: https://doi.org/10.1007/978-1-59745-483-4_13
Published:
Publisher Name: Humana Press, Totowa, NJ
Print ISBN: 978-1-934115-40-4
Online ISBN: 978-1-59745-483-4
eBook Packages: Springer Protocols