Gating of Hydrophobic Nanopores with Large Anions

Polster, Jake W.; Acar, Elif Turker; Aydin, Fikret; Zhan, Cheng; Pham, Tuan Anh; Siwy, Zuzanna S.

doi:10.1021/acsnano.9b09777

Gating of Hydrophobic Nanopores with Large Anions

Journal Article · Tue Mar 17 00:00:00 EDT 2020 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.9b09777· OSTI ID:1844485

Polster, Jake W. ^[1]; Acar, Elif Turker ^[2]; Aydin, Fikret ^[3]; Zhan, Cheng ^[3]; ^[3]; ^[1]

Univ. of California, Irvine, CA (United States)
Univ. of California, Irvine, CA (United States); Istanbul Univ. (Turkey)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

In this report, understanding ion transport in nanoporous materials is critical to a wide variety of energy and environmental technologies, ranging from ion-selective membranes, drug delivery, and biosensing, to ion batteries and supercapacitors. While nanoscale transport is often described by continuum models that rely on a point charge description for ions and a homogeneous dielectric medium for the solvent, here, we show that transport of aqueous solutions at a hydrophobic interface can be highly dependent on the size and hydration strength of the solvated ions. Specifically, measurements of ion current through single silicon nitride nanopores that contain a hydrophobic-hydrophilic junction show that transport properties are dependent not only on applied voltage but also the type of anion. We find that in Cl^- -contained solutions the nanopores only conducted ionic current above a negative voltage threshold. On the other hand, introduction of large polarizable anions, such as Br^- and I^-, facilitated the pore wetting, making the pore conductive at all examined voltages. Molecular dynamics simulations revealed that the large anions, Br^- and I^-, have a weaker solvation shell compared to that of Cl^-, and consequently were prone to migrate from the aqueous solution to the hydrophobic surface, leading to the anion accumulation responsible for pore wetting. The results are essential for designing nanoporous systems that are selective to ions of the same charge, for realization of ion-induced wetting in hydrophobic pores, as well as for fundamental understanding on the role of ion hydration shell on the properties of solid/liquid interfaces.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1844485

Alternate ID(s):: OSTI ID: 1767656

Report Number(s):: LLNL-JRNL-780232; 973962

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 4 Vol. 14; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (71)

Study of Penetration of Water into Hydrophobized Porous Silicas Fadeev, Alexander Y.; Eroshenko, Valentine A. Journal of Colloid and Interface Science, Vol. 187, Issue 2 https://doi.org/10.1006/jcis.1996.4495	journal	March 1997
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Structure in aqueous solutions of nonpolar solutes from the standpoint of scaled-particle theory Stillinger, Frank H. Journal of Solution Chemistry, Vol. 2, Issue 2-3 https://doi.org/10.1007/BF00651970	journal	January 1973
Deconstructing Classical Water Models at Interfaces and in Bulk Remsing, Richard C.; Rodgers, Jocelyn M.; Weeks, John D. Journal of Statistical Physics, Vol. 145, Issue 2 https://doi.org/10.1007/s10955-011-0299-3	journal	August 2011
Numerical integration of the cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes Ryckaert, Jean-Paul; Ciccotti, Giovanni; Berendsen, Herman J. C. Journal of Computational Physics, Vol. 23, Issue 3 https://doi.org/10.1016/0021-9991(77)90098-5	journal	March 1977
Water Dynamics and Dewetting Transitions in the Small Mechanosensitive Channel MscS Anishkin, Andriy; Sukharev, Sergei Biophysical Journal, Vol. 86, Issue 5 https://doi.org/10.1016/S0006-3495(04)74340-4	journal	May 2004
Propensity of soft ions for the air/water interface Vrbka, Lubos; Mucha, Martin; Minofar, Babak Current Opinion in Colloid & Interface Science, Vol. 9, Issue 1-2 https://doi.org/10.1016/j.cocis.2004.05.028	journal	August 2004
Optimization algorithm for the generation of ONCV pseudopotentials Schlipf, Martin; Gygi, François Computer Physics Communications, Vol. 196 https://doi.org/10.1016/j.cpc.2015.05.011	journal	November 2015
Hydrophobic Gating in Ion Channels Aryal, Prafulla; Sansom, Mark S. P.; Tucker, Stephen J. Journal of Molecular Biology, Vol. 427, Issue 1 https://doi.org/10.1016/j.jmb.2014.07.030	journal	January 2015
Salt Solutions in Carbon Nanotubes: The Role of Cation−π Interactions Pham, Tuan Anh; Mortuza, S. M. Golam; Wood, Brandon C. The Journal of Physical Chemistry C, Vol. 120, Issue 13 https://doi.org/10.1021/acs.jpcc.5b12245	journal	March 2016
Concentration-Polarization-Induced Precipitation and Ionic Current Oscillations with Tunable Frequency Acar, Elif Turker; Hinkle, Preston; Siwy, Zuzanna S. The Journal of Physical Chemistry C, Vol. 122, Issue 6 https://doi.org/10.1021/acs.jpcc.7b12265	journal	January 2018
Voltage Gating of a Biomimetic Nanopore: Electrowetting of a Hydrophobic Barrier Trick, Jemma L.; Song, Chen; Wallace, E. Jayne ACS Nano, Vol. 11, Issue 2 https://doi.org/10.1021/acsnano.6b07865	journal	February 2017
In Situ Nanopore Fabrication and Single-Molecule Sensing with Microscale Liquid Contacts Arcadia, Christopher E.; Reyes, Carlos C.; Rosenstein, Jacob K. ACS Nano, Vol. 11, Issue 5 https://doi.org/10.1021/acsnano.7b01519	journal	April 2017
Effect of Field Direction on Electrowetting in a Nanopore Bratko, Dusan; Daub, Christopher D.; Leung, Kevin Journal of the American Chemical Society, Vol. 129, Issue 9 https://doi.org/10.1021/ja0659370	journal	March 2007
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
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian Journal of the American Chemical Society, Vol. 118, Issue 45 https://doi.org/10.1021/ja9621760	journal	January 1996
Introducing Chemical Transport Selectivity into Gold Nanotubule Membranes Hulteen, John C.; Jirage, Kshama B.; Martin, Charles R. Journal of the American Chemical Society, Vol. 120, Issue 26 https://doi.org/10.1021/ja980045o	journal	July 1998
Charge Inversion and Calcium Gating in Mixtures of Ions in Nanopores Lin, Kabin; Lin, Chih-Yuan; Polster, Jake W. Journal of the American Chemical Society, Vol. 142, Issue 6 https://doi.org/10.1021/jacs.9b11537	journal	January 2020
Perfluoroalkanes: Conformational Analysis and Liquid-State Properties from ab Initio and Monte Carlo Calculations Watkins, Edward K.; Jorgensen, William L. The Journal of Physical Chemistry A, Vol. 105, Issue 16 https://doi.org/10.1021/jp004071w	journal	April 2001
Molecular Mechanism of Ion Binding to the Liquid/Vapor Interface of Water Dang, Liem X.; Chang, Tsun-Mei The Journal of Physical Chemistry B, Vol. 106, Issue 2 https://doi.org/10.1021/jp011853w	journal	January 2002
Molecular Structure of Salt Solutions: A New View of the Interface with Implications for Heterogeneous Atmospheric Chemistry Jungwirth, Pavel; Tobias, Douglas J. The Journal of Physical Chemistry B, Vol. 105, Issue 43 https://doi.org/10.1021/jp012750g	journal	November 2001
Ions at the Air/Water Interface Jungwirth, Pavel; Tobias, Douglas J. The Journal of Physical Chemistry B, Vol. 106, Issue 25 https://doi.org/10.1021/jp020242g	journal	June 2002
Computational Study of Ion Binding to the Liquid Interface of Water ^† Dang, Liem X. The Journal of Physical Chemistry B, Vol. 106, Issue 40 https://doi.org/10.1021/jp021871t	journal	October 2002
Vibrational Spectroscopy of Aqueous Sodium Halide Solutions and Air−Liquid Interfaces: Observation of Increased Interfacial Depth Liu, Dingfang; Ma, Gang; Levering, Lori M. The Journal of Physical Chemistry B, Vol. 108, Issue 7 https://doi.org/10.1021/jp036169r	journal	February 2004
Probing the Interfacial Structure of Aqueous Electrolytes with Femtosecond Second Harmonic Generation Spectroscopy Petersen, Poul B.; Saykally, Richard J. The Journal of Physical Chemistry B, Vol. 110, Issue 29 https://doi.org/10.1021/jp0601825	journal	July 2006
Hydration Behavior under Confinement by Nanoscale Surfaces with Patterned Hydrophobicity and Hydrophilicity Giovambattista, Nicolas; Debenedetti, Pablo G.; Rossky, Peter J. The Journal of Physical Chemistry C, Vol. 111, Issue 3 https://doi.org/10.1021/jp065419b	journal	December 2006
Sitting at the Edge: How Biomolecules use Hydrophobicity to Tune Their Interactions and Function Patel, Amish J.; Varilly, Patrick; Jamadagni, Sumanth N. The Journal of Physical Chemistry B, Vol. 116, Issue 8 https://doi.org/10.1021/jp2107523	journal	February 2012
Fluctuations of Water near Extended Hydrophobic and Hydrophilic Surfaces Patel, Amish J.; Varilly, Patrick; Chandler, David The Journal of Physical Chemistry B, Vol. 114, Issue 4 https://doi.org/10.1021/jp909048f	journal	February 2010
Surface Propensities of Atmospherically Relevant Ions in Salt Solutions Revealed by Phase-Sensitive Sum Frequency Vibrational Spectroscopy Tian, Chuanshan; Byrnes, Steven J.; Han, Hui-Ling The Journal of Physical Chemistry Letters, Vol. 2, Issue 15 https://doi.org/10.1021/jz200791c	journal	July 2011
Ions at Hydrophobic Aqueous Interfaces: Molecular Dynamics with Effective Polarization Vazdar, Mario; Pluhařová, Eva; Mason, Phil E. The Journal of Physical Chemistry Letters, Vol. 3, Issue 15 https://doi.org/10.1021/jz300805b	journal	July 2012
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
Water Confinement in Hydrophobic Nanopores. Pressure-Induced Wetting and Drying Smirnov, Sergei; Vlassiouk, Ivan; Takmakov, Pavel ACS Nano, Vol. 4, Issue 9 https://doi.org/10.1021/nn101080k	journal	August 2010
Voltage-Gated Hydrophobic Nanopores Smirnov, Sergei N.; Vlassiouk, Ivan V.; Lavrik, Nickolay V. ACS Nano, Vol. 5, Issue 9 https://doi.org/10.1021/nn202392d	journal	August 2011
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
Surface topography dependence of biomolecular hydrophobic hydration Cheng, Yuen-Kit; Rossky, Peter J. Nature, Vol. 392, Issue 6677 https://doi.org/10.1038/33653	journal	April 1998
Voltage-dependent ordering of water molecules at an electrode–electrolyte interface Toney, Michael F.; Howard, Jason N.; Richer, Jocelyn Nature, Vol. 368, Issue 6470 https://doi.org/10.1038/368444a0	journal	March 1994
Interfaces and the driving force of hydrophobic assembly Chandler, David Nature, Vol. 437, Issue 7059 https://doi.org/10.1038/nature04162	journal	September 2005
Modulation of hydrophobic interactions by proximally immobilized ions Ma, C. Derek; Wang, Chenxuan; Acevedo-Vélez, Claribel Nature, Vol. 517, Issue 7534 https://doi.org/10.1038/nature14018	journal	January 2015
Electric-field-induced wetting and dewetting in single hydrophobic nanopores Powell, Matthew R.; Cleary, Leah; Davenport, Matthew Nature Nanotechnology, Vol. 6, Issue 12 https://doi.org/10.1038/nnano.2011.189	journal	October 2011
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
Presence of electrolyte promotes wetting and hydrophobic gating in nanopores with residual surface charges Innes, Laura; Gutierrez, Diego; Mann, William The Analyst, Vol. 140, Issue 14 https://doi.org/10.1039/C4AN02244K	journal	January 2015
Continuous assembly of supramolecular polyamine–phosphate networks on surfaces: preparation and permeability properties of nanofilms Agazzi, Maximiliano L.; Herrera, Santiago E.; Cortez, M. Lorena Soft Matter, Vol. 15, Issue 7 https://doi.org/10.1039/C8SM02387E	journal	January 2019
Ion spatial distributions at the liquid–vapor interface of aqueous potassium fluoride solutions Brown, Matthew A.; D’Auria, Raffaella; Kuo, I. -F. William Physical Chemistry Chemical Physics, Vol. 10, Issue 32 https://doi.org/10.1039/b807041e	journal	January 2008
Specific ion effects in aqueous eletrolyte solutions confined within graphene sheets at the nanometric scale Sala, J.; Guàrdia, E.; Martí, J. Physical Chemistry Chemical Physics, Vol. 14, Issue 30 https://doi.org/10.1039/c2cp40537g	journal	January 2012
Towards an assessment of the accuracy of density functional theory for first principles simulations of water Grossman, Jeffrey C.; Schwegler, Eric; Draeger, Erik W. The Journal of Chemical Physics, Vol. 120, Issue 1 https://doi.org/10.1063/1.1630560	journal	January 2004
Intrusion and extrusion of water in hydrophobic mesopores Lefevre, B.; Saugey, A.; Barrat, J. L. The Journal of Chemical Physics, Vol. 120, Issue 10 https://doi.org/10.1063/1.1643728	journal	March 2004
Towards an assessment of the accuracy of density functional theory for first principles simulations of water. II Schwegler, Eric; Grossman, Jeffrey C.; Gygi, François The Journal of Chemical Physics, Vol. 121, Issue 11 https://doi.org/10.1063/1.1782074	journal	September 2004
Electric-field-controlled water and ion permeation of a hydrophobic nanopore Dzubiella, J.; Hansen, J. -P. The Journal of Chemical Physics, Vol. 122, Issue 23 https://doi.org/10.1063/1.1927514	journal	June 2005
A unified formulation of the constant temperature molecular dynamics methods Nosé, Shuichi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447334	journal	July 1984
Molecular dynamics with coupling to an external bath Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F. The Journal of Chemical Physics, Vol. 81, Issue 8 https://doi.org/10.1063/1.448118	journal	October 1984
The molecular structure of the interface between water and a hydrophobic substrate is liquid-vapor like Willard, Adam P.; Chandler, David The Journal of Chemical Physics, Vol. 141, Issue 18 https://doi.org/10.1063/1.4897249	journal	November 2014
Structure and dynamics of aqueous solutions from PBE-based first-principles molecular dynamics simulations Pham, Tuan Anh; Ogitsu, Tadashi; Lau, Edmond Y. The Journal of Chemical Physics, Vol. 145, Issue 15 https://doi.org/10.1063/1.4964865	journal	October 2016
Anisotropic structure and dynamics of water under static electric fields Shafiei, Mahdi; von Domaros, Michael; Bratko, Dusan The Journal of Chemical Physics, Vol. 150, Issue 7 https://doi.org/10.1063/1.5079393	journal	February 2019
Liquid-vapor oscillations of water in hydrophobic nanopores Beckstein, O.; Sansom, M. S. P. Proceedings of the National Academy of Sciences, Vol. 100, Issue 12 https://doi.org/10.1073/pnas.1136844100	journal	May 2003
Solvent fluctuations in hydrophobic cavity–ligand binding kinetics Setny, Piotr; Baron, Riccardo; Michael Kekenes-Huskey, Peter Proceedings of the National Academy of Sciences, Vol. 110, Issue 4 https://doi.org/10.1073/pnas.1221231110	journal	January 2013
Mechanism of ion adsorption to aqueous interfaces: Graphene/water vs. air/water McCaffrey, Debra L.; Nguyen, Son C.; Cox, Stephen J. Proceedings of the National Academy of Sciences, Vol. 114, Issue 51 https://doi.org/10.1073/pnas.1702760114	journal	August 2017
Intrusion and extrusion of water in hydrophobic nanopores Tinti, Antonio; Giacomello, Alberto; Grosu, Yaroslav Proceedings of the National Academy of Sciences, Vol. 114, Issue 48 https://doi.org/10.1073/pnas.1714796114	journal	November 2017
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
Hydration properties of mechanosensitive channel pores define the energetics of gating Anishkin, A.; Akitake, B.; Kamaraju, K. Journal of Physics: Condensed Matter, Vol. 22, Issue 45 https://doi.org/10.1088/0953-8984/22/45/454120	journal	October 2010
Comparison of bipolar and unipolar ionic diodes Nguyen, Gael; Vlassiouk, Ivan; Siwy, Zuzanna S. Nanotechnology, Vol. 21, Issue 26 https://doi.org/10.1088/0957-4484/21/26/265301	journal	June 2010
A hydrophobic gate in an ion channel: the closed state of the nicotinic acetylcholine receptor Beckstein, Oliver; Sansom, Mark S. P. Physical Biology, Vol. 3, Issue 2 https://doi.org/10.1088/1478-3975/3/2/007	journal	June 2006
Canonical dynamics: Equilibrium phase-space distributions Hoover, William G. Physical Review A, Vol. 31, Issue 3 https://doi.org/10.1103/PhysRevA.31.1695	journal	March 1985
Giant Osmotic Pressure in the Forced Wetting of Hydrophobic Nanopores Michelin-Jamois, Millan; Picard, Cyril; Vigier, Gérard Physical Review Letters, Vol. 115, Issue 3 https://doi.org/10.1103/PhysRevLett.115.036101	journal	July 2015
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Ion-Specific Anomalous Electrokinetic Effects in Hydrophobic Nanochannels Huang, David M.; Cottin-Bizonne, Cécile; Ybert, Christophe Physical Review Letters, Vol. 98, Issue 17 https://doi.org/10.1103/PhysRevLett.98.177801	journal	April 2007
Transport phenomena in nanofluidics Schoch, Reto B.; Han, Jongyoon; Renaud, Philippe Reviews of Modern Physics, Vol. 80, Issue 3 https://doi.org/10.1103/RevModPhys.80.839	journal	July 2008
Electron Spectroscopy of Aqueous Solution Interfaces Reveals Surface Enhancement of Halides Ghosal, S. Science, Vol. 307, Issue 5709 https://doi.org/10.1126/science.1106525	journal	January 2005
On the Nature of ions at the Liquid Water Surface Petersen, Poul B.; Saykally, Richard J. Annual Review of Physical Chemistry, Vol. 57, Issue 1 https://doi.org/10.1146/annurev.physchem.57.032905.104609	journal	May 2006
Architecture of Qbox: A scalable first-principles molecular dynamics code Gygi, F. IBM Journal of Research and Development, Vol. 52, Issue 1.2 https://doi.org/10.1147/rd.521.0137	journal	January 2008
Nanopore Fabrication by Controlled Dielectric Breakdown Kwok, Harold; Briggs, Kyle; Tabard-Cossa, Vincent PLoS ONE, Vol. 9, Issue 3 https://doi.org/10.1371/journal.pone.0092880	journal	March 2014
The Hydrophobic Effect Contributes to the Closed State of a Simplified Ion Channel through a Conserved Hydrophobic Patch at the Pore-Helix Crossing Yonkunas, Michael; Kurnikova, Maria Frontiers in Pharmacology, Vol. 6 https://doi.org/10.3389/fphar.2015.00284	journal	November 2015

Similar Records

Voltage-Gated Hydrophobic Nanopores

Journal Article · Fri Dec 31 23:00:00 EST 2010 · ACS Nano · OSTI ID:1024323

Atomistic Insight on the Charging Energetics in Sub-nanometer Pore Supercacitors

Journal Article · Thu Dec 31 23:00:00 EST 2009 · Journal of Physical Chemistry C · OSTI ID:991682

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
first principles calculations.
hydrophobic interface
ion current gating
molecular dynamics simulations
wettability

Gating of Hydrophobic Nanopores with Large Anions

Citation Formats

References (71)

Similar Records

Related Subjects