Polarization of gold in nanopores leads to ion current rectification

Yang, Crystal; Hinkle, Preston; Menestrina, Justin; Vlassiouk, Ivan V.; Siwy, Zuzanna S.

doi:10.1021/acs.jpclett.6b01971

Polarization of gold in nanopores leads to ion current rectification

Journal Article · Mon Oct 03 00:00:00 EDT 2016 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.6b01971· OSTI ID:1344289

Yang, Crystal ^[1]; Hinkle, Preston ^[1]; Menestrina, Justin ^[1]; Vlassiouk, Ivan V. ^[2]; Siwy, Zuzanna S. ^[1]

Univ. of California, Irvine, CA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Biomimetic nanopores with rectifying properties are relevant components of ionic switches, ionic circuits, and biological sensors. Rectification indicates that currents for voltages of one polarity are higher than currents for voltages of the opposite polarity. Ion current rectification requires the presence of surface charges on the pore walls, achieved either by the attachment of charged groups or in multielectrode systems by applying voltage to integrated gate electrodes. Here we present a simpler concept for introducing surface charges via polarization of a thin layer of Au present at one entrance of a silicon nitride nanopore. In an electric field applied by two electrodes placed in bulk solution on both sides of the membrane, the Au layer polarizes such that excess positive charge locally concentrates at one end and negative charge concentrates at the other end. Consequently, a junction is formed between zones with enhanced anion and cation concentrations in the solution adjacent to the Au layer. This bipolar double layer together with enhanced cation concentration in a negatively charged silicon nitride nanopore leads to voltage-controlled surface-charge patterns and ion current rectification. The experimental findings are supported by numerical modeling that confirm modulation of ionic concentrations by the Au layer and ion current rectification even in low-aspect ratio nanopores. Lastly, our findings enable a new strategy for creating ionic circuits with diodes and transistors.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: ORNL LDRD Director's R&D; USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1344289

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 20 Vol. 7; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (47)

Ion-Current Rectification in Nanopores and Nanotubes with Broken Symmetry Siwy, Z. S. Advanced Functional Materials, Vol. 16, Issue 6 https://doi.org/10.1002/adfm.200500471	journal	April 2006
Nanofluidic Bipolar Transistors Kalman, E. B.; Vlassiouk, I.; Siwy, Z. S. Advanced Materials, Vol. 20, Issue 2 https://doi.org/10.1002/adma.200701867	journal	January 2008
On the adsorption of aliphatic alcohols on gold Holze, Rudolf; Beŧowska-Brzezinska, Maria Electrochimica Acta, Vol. 30, Issue 7 https://doi.org/10.1016/0013-4686(85)80153-5	journal	July 1985
Determination of surface charge density parameters of silicon nitride Sonnefeld, J. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 108, Issue 1 https://doi.org/10.1016/0927-7757(95)03356-4	journal	March 1996
Electro-oxidation of ethanol on gold: analysis of the reaction products and mechanism Tremiliosi-Filho, G.; Gonzalez, E. R.; Motheo, A. J. Journal of Electroanalytical Chemistry, Vol. 444, Issue 1 https://doi.org/10.1016/S0022-0728(97)00536-6	journal	March 1998
Induced-charge electro-osmosis Squires, Todd M.; Bazant, Martin Z. Journal of Fluid Mechanics, Vol. 509 https://doi.org/10.1017/S0022112004009309	journal	January 1999
A Theoretical and Experimental Framework for Understanding Electrogenerated Chemiluminescence (ECL) Emission at Bipolar Electrodes Mavré, François; Chow, Kwok-Fan; Sheridan, Eoin Analytical Chemistry, Vol. 81, Issue 15 https://doi.org/10.1021/ac900744p	journal	August 2009
Current Rectification at Quartz Nanopipet Electrodes Wei, Chang; Bard, Allen J.; Feldberg, Stephen W. Analytical Chemistry, Vol. 69, Issue 22 https://doi.org/10.1021/ac970551g	journal	November 1997
Bioinspired Smart Gate-Location-Controllable Single Nanochannels: Experiment and Theoretical Simulation Zhang, Huacheng; Tian, Ye; Hou, Jue ACS Nano, Vol. 9, Issue 12 https://doi.org/10.1021/acsnano.5b05542	journal	October 2015
Asymmetric Ion Transport through Ion-Channel-Mimetic Solid-State Nanopores Guo, Wei; Tian, Ye; Jiang, Lei Accounts of Chemical Research, Vol. 46, Issue 12 https://doi.org/10.1021/ar400024p	journal	January 2013
The Dielectric Constant of Mixtures of Ethyl Alcohol and Water from -5 to 40° Wyman, Jeffries. Journal of the American Chemical Society, Vol. 53, Issue 9 https://doi.org/10.1021/ja01360a012	journal	September 1931
Protein Biosensors Based on Biofunctionalized Conical Gold Nanotubes Siwy, Zuzanna; Trofin, Lacramioara; Kohli, Punit Journal of the American Chemical Society, Vol. 127, Issue 14 https://doi.org/10.1021/ja043910f	journal	April 2005
Conical-Nanotube Ion-Current Rectifiers: The Role of Surface Charge Siwy, Zuzanna; Heins, Elizabeth; Harrell, C. Chad Journal of the American Chemical Society, Vol. 126, Issue 35 https://doi.org/10.1021/ja047675c	journal	September 2004
Electrokinetics in Microfluidic Channels Containing a Floating Electrode Dhopeshwarkar, Rahul; Hlushkou, Dzmitry; Nguyen, Mark Journal of the American Chemical Society, Vol. 130, Issue 32, p. 10480-10481 https://doi.org/10.1021/ja8036405	journal	August 2008
Single Conical Nanopores Displaying pH-Tunable Rectifying Characteristics. Manipulating Ionic Transport With Zwitterionic Polymer Brushes Yameen, Basit; Ali, Mubarak; Neumann, Reinhard Journal of the American Chemical Society, Vol. 131, Issue 6 https://doi.org/10.1021/ja8086104	journal	February 2009
Biosensing with Nanofluidic Diodes Vlassiouk, Ivan; Kozel, Thomas R.; Siwy, Zuzanna S. Journal of the American Chemical Society, Vol. 131, Issue 23 https://doi.org/10.1021/ja901120f	journal	June 2009
Electrooxidation of Ethanol and Methanol Using the Molecular Catalyst [{Ru ₄ O ₄ (OH) ₂ (H ₂ O) ₄ }(γ-SiW ₁₀ O ₃₆ ) ₂ ] ^10– Liu, YuPing; Zhao, Shu-Feng; Guo, Si-Xuan Journal of the American Chemical Society, Vol. 138, Issue 8 https://doi.org/10.1021/jacs.5b11408	journal	February 2016
Noise Properties of Rectifying Nanopores Powell, M. R.; Sa, N.; Davenport, M. The Journal of Physical Chemistry C, Vol. 115, Issue 17 https://doi.org/10.1021/jp2016038	journal	April 2011
Understanding the Oxidative Stability of Gold Monolayer-Protected Clusters in the Presence of Halide Ions under Ambient Conditions Dasog, Mita; Scott, Robert W. J. Langmuir, Vol. 23, Issue 6 https://doi.org/10.1021/la0627415	journal	March 2007
Ion Current Rectification at Nanopores in Glass Membranes White, Henry S.; Bund, Andreas Langmuir, Vol. 24, Issue 5 https://doi.org/10.1021/la702955k	journal	March 2008
Logic Gates Using Nanofluidic Diodes Based on Conical Nanopores Functionalized with Polyprotic Acid Chains Ali, Mubarak; Mafe, Salvador; Ramirez, Patricio Langmuir, Vol. 25, Issue 20 https://doi.org/10.1021/la902792f	journal	October 2009
Electrochemistry on a Localized Surface Plasmon Resonance Sensor Sannomiya, Takumi; Dermutz, Harald; Hafner, Christian Langmuir, Vol. 26, Issue 10 https://doi.org/10.1021/la9042342	journal	May 2010
Nanofluidic Diode and Bipolar Transistor Daiguji, Hirofumi; Oka, Yukiko; Shirono, Katsuhiro Nano Letters, Vol. 5, Issue 11 https://doi.org/10.1021/nl051646y	journal	November 2005
Rectification of Ionic Current in a Nanofluidic Diode Karnik, Rohit; Duan, Chuanhua; Castelino, Kenneth Nano Letters, Vol. 7, Issue 3 https://doi.org/10.1021/nl062806o	journal	March 2007
Nanofluidic Diode Vlassiouk, Ivan; Siwy, Zuzanna S. Nano Letters, Vol. 7, Issue 3 https://doi.org/10.1021/nl062924b	journal	March 2007
p − n Semiconductor Membrane for Electrically Tunable Ion Current Rectification and Filtering Gracheva, Maria E.; Vidal, Julien; Leburton, Jean-Pierre Nano Letters, Vol. 7, Issue 6 https://doi.org/10.1021/nl0707104	journal	June 2007
Ionic Field Effect Transistors with Sub-10 nm Multiple Nanopores Nam, Sung-Wook; Rooks, Michael J.; Kim, Ki-Bum Nano Letters, Vol. 9, Issue 5 https://doi.org/10.1021/nl900309s	journal	May 2009
Nanofluidic Ionic Diodes. Comparison of Analytical and Numerical Solutions Vlassiouk, Ivan; Smirnov, Sergei; Siwy, Zuzanna ACS Nano, Vol. 2, Issue 8 https://doi.org/10.1021/nn800306u	journal	July 2008
Multilayered Semiconductor Membranes for Nanopore Ionic Conductance Modulation Gracheva, Maria E.; Melnikov, Dmitriy V.; Leburton, Jean-Pierre ACS Nano, Vol. 2, Issue 11 https://doi.org/10.1021/nn8004679	journal	November 2008
A pH-Tunable Nanofluidic Diode with a Broad Range of Rectifying Properties Ali, Mubarak; Ramirez, Patricio; Mafé, Salvador ACS Nano, Vol. 3, Issue 3 https://doi.org/10.1021/nn900039f	journal	February 2009
Field-effect reconfigurable nanofluidic ionic diodes Guan, Weihua; Fan, Rong; Reed, Mark A. Nature Communications, Vol. 2, Issue 1 https://doi.org/10.1038/ncomms1514	journal	September 2011
Fabrication of solid-state nanopores with single-nanometre precision Storm, A. J.; Chen, J. H.; Ling, X. S. Nature Materials, Vol. 2, Issue 8, p. 537-540 https://doi.org/10.1038/nmat941	journal	July 2003
Droplet networks with incorporated protein diodes show collective properties Maglia, Giovanni; Heron, Andrew J.; Hwang, William L. Nature Nanotechnology, Vol. 4, Issue 7 https://doi.org/10.1038/nnano.2009.121	journal	June 2009
Engineered voltage-responsive nanopores Siwy, Zuzanna S.; Howorka, Stefan Chem. Soc. Rev., Vol. 39, Issue 3 https://doi.org/10.1039/B909105J	journal	January 2010
Electric field gradient focusing in microchannels with embedded bipolar electrode Hlushkou, Dzmitry; Perdue, Robbyn K.; Dhopeshwarkar, Rahul Lab on a Chip, Vol. 9, Issue 13 https://doi.org/10.1039/b822404h	journal	January 2009
Biomimetic smart nanopores and nanochannels Hou, Xu; Guo, Wei; Jiang, Lei Chemical Society Reviews, Vol. 40, Issue 5 https://doi.org/10.1039/c0cs00053a	journal	January 2011
A hydrophobic entrance enhances ion current rectification and induces dewetting in asymmetric nanopores Pevarnik, Matthew; Healy, Ken; Davenport, Matthew The Analyst, Vol. 137, Issue 13 https://doi.org/10.1039/c2an16139g	journal	January 2012
Rectification properties of conically shaped nanopores: consequences of miniaturization Pietschmann, J. -F.; Wolfram, M. -T.; Burger, M. Physical Chemistry Chemical Physics, Vol. 15, Issue 39 https://doi.org/10.1039/c3cp53105h	journal	January 2013
Noise in solid-state nanopores Smeets, R. M. M.; Keyser, U. F.; Dekker, N. H. Proceedings of the National Academy of Sciences, Vol. 105, Issue 2 https://doi.org/10.1073/pnas.0705349105	journal	January 2008
Ion bipolar junction transistors Tybrandt, K.; Larsson, K. C.; Richter-Dahlfors, A. Proceedings of the National Academy of Sciences, Vol. 107, Issue 22 https://doi.org/10.1073/pnas.0913911107	journal	May 2010
Access resistance of a small circular pore Hall, J. E. The Journal of General Physiology, Vol. 66, Issue 4 https://doi.org/10.1085/jgp.66.4.531	journal	October 1975
Characteristics of solid-state nanometre pores fabricated using a transmission electron microscope Kim, Min Jun; McNally, Ben; Murata, Kazuyoshi Nanotechnology, Vol. 18, Issue 20 https://doi.org/10.1088/0957-4484/18/20/205302	journal	April 2007
Induced Charge Electro-osmosis over Controllably Contaminated Electrodes Pascall, Andrew J.; Squires, Todd M. Physical Review Letters, Vol. 104, Issue 8 https://doi.org/10.1103/PhysRevLett.104.088301	journal	February 2010
Fabrication of a Synthetic Nanopore Ion Pump Siwy, Z.; Fuliński, A. Physical Review Letters, Vol. 89, Issue 19 https://doi.org/10.1103/PhysRevLett.89.198103	journal	October 2002
Metal Nanotubule Membranes with Electrochemically Switchable Ion-Transport Selectivity Nishizawa, M.; Menon, V. P.; Martin, C. R. Science, Vol. 268, Issue 5211 https://doi.org/10.1126/science.268.5211.700	journal	May 1995
Mechanisms for Ethanol Electrooxidation on Pt(111) and Adsorption Bond Strengths Defining an Ideal Catalyst Asiri, Haleema Aied; Anderson, Alfred B. Journal of The Electrochemical Society, Vol. 162, Issue 1 https://doi.org/10.1149/2.0781501jes	journal	November 2014
A Poisson/Nernst-Planck model for ionic transport through synthetic conical nanopores Cervera, J.; Schiedt, B.; Ramírez, P. Europhysics Letters (EPL), Vol. 71, Issue 1 https://doi.org/10.1209/epl/i2005-10054-x	journal	July 2005

Cited By (6)

Direct electrochemical observation of glucosidase activity in isolated single lysosomes from a living cell Pan, Rongrong; Xu, Mingchen; Burgess, James D. Proceedings of the National Academy of Sciences, Vol. 115, Issue 16 https://doi.org/10.1073/pnas.1719844115	journal	April 2018
Dynamic Curvature Nanochannel‐Based Membrane with Anomalous Ionic Transport Behaviors and Reversible Rectification Switch Wang, Miao; Meng, Haiqiang; Wang, Dan Advanced Materials, Vol. 31, Issue 11 https://doi.org/10.1002/adma.201805130	journal	January 2019
A review: applications of ion transport in micro‐nanofluidic systems based on ion concentration polarization Han, Wenbo; Chen, Xueye Journal of Chemical Technology & Biotechnology, Vol. 95, Issue 6 https://doi.org/10.1002/jctb.6288	journal	December 2019
A novel design of nanochannel structure in a micro–nanofluidic preconcentrator for electrokinetic ion enrichment Han, Wenbo; Chen, Xueye Journal of the Brazilian Society of Mechanical Sciences and Engineering, Vol. 42, Issue 1 https://doi.org/10.1007/s40430-019-2136-6	journal	December 2019
A simple strategy for the fabrication of gold-modified single nanopores and its application for miRNA sensing Yang, Cheng; Wang, Hao; Tang, Haoran Chemical Communications, Vol. 55, Issue 69 https://doi.org/10.1039/c9cc04864b	journal	January 2019
Induced-Charge Enhancement of the Diffusion Potential in Membranes with Polarizable Nanopores Ryzhkov, I. I.; Lebedev, D. V.; Solodovnichenko, V. S. Physical Review Letters, Vol. 119, Issue 22 https://doi.org/10.1103/physrevlett.119.226001	journal	November 2017

Similar Records

Current rectification for transport of room-temperature ionic liquids through conical nanopores

Journal Article · Mon Feb 08 19:00:00 EST 2016 · Journal of Physical Chemistry. C · OSTI ID:1339300

Ion concentration polarization causes a nearly pore-length-independent conductance of nanopores

Journal Article · Wed Aug 07 20:00:00 EDT 2024 · Faraday Discussions · OSTI ID:3002051

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Polarization of gold in nanopores leads to ion current rectification

Citation Formats

References (47)

Cited By (6)

Similar Records

Related Subjects