Ion Gating in Nanopore Electrode Arrays with Hierarchically Organized pH-Responsive Block Copolymer Membranes

Baek, Seol; Kwon, Seung-Ryong; Fu, Kaiyu; Bohn, Paul W.

doi:10.1021/acsami.0c12926

Title: Ion Gating in Nanopore Electrode Arrays with Hierarchically Organized pH-Responsive Block Copolymer Membranes

Journal Article · Sat Nov 21 00:00:00 EST 2020 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.0c12926· OSTI ID:1737368

Baek, Seol ^[1];

^[1];

^[2];

^[1]

Univ. of Notre Dame, IN (United States)
Stanford Univ., CA (United States)

Inspired by biological ion channels, artificial nanopore-based architectures have been developed for smart ion/molecular transport control with potential applications to iontronics and energy conversion. Advances in nanofabrication technology enable simple, versatile construction methods, and post-fabrication functionalization delivers nanochannels with unique ion transport-control attributes. Here, we characterize a pH-responsive, charge-selective dual-gating block copolymer (BCP) membrane composed of polystyrene-b-poly(4-vinylpyridine) (PS₄₈₄₀₀-b-P4VP₂₁₃₀₀), capable of self-organizing into highly ordered nanocylindrical domains. Because the PS-b-P4VP membrane exhibits pH-dependent structural transitions, it is suitable for designing intelligent pH-gated biomimetic channels, for example, exhibiting on–off transport switching at pH values near the pK_a of P4VP with excellent anion permselectivity at pH < pK_a. Introducing the BCP membrane onto nanopore electrode arrays (BCP@NEAs) allows the BCP to serve as a pH-responsive gate controlling ion transfer into the NEA nanopores. Such selectively transported and confined ions are detected by using a 100 nm gap dual-ring nanoelectrode structure capable of enhancing current output by efficient redox cycling with an amplification factor >10². In addition, BCP@NEAs exhibit extraordinary pH-gated ion selectivity, resulting in a 3380-fold current difference between anion and cation probes at pH 3.0. Furthermore, this hierarchically organized BCP-gated NEA system can serve as a template for the development of other stimulus-responsive ion gates, for example, those based on temperature and ligand gating, thus exploiting the intrinsic advantages of NEAs, such as enhanced sensitivity based on redox cycling, which may lead to technological applications such as engineered biosensors and iontronic devices.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Univ. of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: FG02-07ER15851

OSTI ID:: 1737368

Journal Information:: ACS Applied Materials and Interfaces, Vol. 12, Issue 49; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (53)

The Structure of the Potassium Channel: Molecular Basis of K+ Conduction and Selectivity Doyle, D. A. Science, Vol. 280, Issue 5360 https://doi.org/10.1126/science.280.5360.69	journal	April 1998
Principles of Selective Ion Transport in Channels and Pumps Gouaux, E. Science, Vol. 310, Issue 5753 https://doi.org/10.1126/science.1113666	journal	December 2005
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
Highly Efficient Gating of Electrically Actuated Nanochannels for Pulsatile Drug Delivery Stemming from a Reversible Wettability Switch Zhang, Qianqian; Kang, Jianxin; Xie, Zhiqiang Advanced Materials, Vol. 30, Issue 4 https://doi.org/10.1002/adma.201703323	journal	December 2017
Biomimetic membranes: A review Shen, Yue-xiao; Saboe, Patrick O.; Sines, Ian T. Journal of Membrane Science, Vol. 454 https://doi.org/10.1016/j.memsci.2013.12.019	journal	March 2014
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
Interface Design of Nanochannels for Energy Utilization Zhu, Yinglin; Zhan, Kan; Hou, Xu ACS Nano, Vol. 12, Issue 2 https://doi.org/10.1021/acsnano.7b07923	journal	January 2018
Smart Gating Multi-Scale Pore/Channel-Based Membranes Hou, Xu Advanced Materials, Vol. 28, Issue 33 https://doi.org/10.1002/adma.201600797	journal	June 2016
Engineering of thermo-/pH-responsive membranes with enhanced gating coefficients, reversible behaviors and self-cleaning performance through acetic acid boosted microgel assembly Liu, Huawen; Zhao, Xueting; Jia, Ning Journal of Materials Chemistry A, Vol. 6, Issue 25 https://doi.org/10.1039/C8TA04010A	journal	January 2018
Fundamental studies and practical applications of bio-inspired smart solid-state nanopores and nanochannels Zhang, Huacheng; Tian, Ye; Jiang, Lei Nano Today, Vol. 11, Issue 1 https://doi.org/10.1016/j.nantod.2015.11.001	journal	February 2016
Solid-state nanopore based biomimetic voltage gated ion channels Pevarnik, Matthew; Cui, Weibin; Yemenicioglu, Sukru Bioinspiration & Biomimetics, Vol. 12, Issue 6 https://doi.org/10.1088/1748-3190/aa811b	journal	November 2017
Biomimetic potassium-selective nanopores Acar, Elif Turker; Buchsbaum, Steven F.; Combs, Cody Science Advances, Vol. 5, Issue 2 https://doi.org/10.1126/sciadv.aav2568	journal	February 2019
Recent Advances in Solid Nanopore/Channel Analysis Long, Zi; Zhan, Shenshan; Gao, Pengcheng Analytical Chemistry, Vol. 90, Issue 1 https://doi.org/10.1021/acs.analchem.7b04737	journal	December 2017
Thermo- and pH-responsive graphene oxide membranes with tunable nanochannels for water gating and permeability of small molecules Liu, Huawen; Zhu, Jiajie; Hao, Liang Journal of Membrane Science, Vol. 587 https://doi.org/10.1016/j.memsci.2019.06.003	journal	October 2019
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
Control of Nanopore Wetting by a Photochromic Spiropyran: A Light-Controlled Valve and Electrical Switch Vlassiouk, Ivan; Park, Choong-Do; Vail, Sean A. Nano Letters, Vol. 6, Issue 5 https://doi.org/10.1021/nl060313d	journal	May 2006
Electrowetting‐Mediated Transport to Produce Electrochemical Transistor Action in Nanopore Electrode Arrays Kwon, Seung‐Ryong; Baek, Seol; Fu, Kaiyu Small, Vol. 16, Issue 18 https://doi.org/10.1002/smll.201907249	journal	April 2020
Isoporous Block Copolymer Membranes Abetz, Volker Macromolecular Rapid Communications, Vol. 36, Issue 1 https://doi.org/10.1002/marc.201400556	journal	November 2014
Polydispersity and block copolymer self-assembly Lynd, Nathaniel A.; Meuler, Adam J.; Hillmyer, Marc A. Progress in Polymer Science, Vol. 33, Issue 9 https://doi.org/10.1016/j.progpolymsci.2008.07.003	journal	September 2008
Patterning with block copolymer thin films Segalman, Rachel A. Materials Science and Engineering: R: Reports, Vol. 48, Issue 6, p. 191-226 https://doi.org/10.1016/j.mser.2004.12.003	journal	February 2005
A Bioinspired Multifunctional Heterogeneous Membrane with Ultrahigh Ionic Rectification and Highly Efficient Selective Ionic Gating Zhang, Zhen; Kong, Xiang-Yu; Xiao, Kai Advanced Materials, Vol. 28, Issue 1 https://doi.org/10.1002/adma.201503668	journal	November 2015
Selective Separation of Similarly Sized Proteins with Tunable Nanoporous Block Copolymer Membranes Qiu, Xiaoyan; Yu, Haizhou; Karunakaran, Madhavan ACS Nano, Vol. 7, Issue 1 https://doi.org/10.1021/nn305073e	journal	December 2012
Smart Bioinspired Nanochannels and their Applications in Energy-Conversion Systems Li, Ruirui; Fan, Xia; Liu, Zhaoyue Advanced Materials, Vol. 29, Issue 45 https://doi.org/10.1002/adma.201702983	journal	August 2017
Stimuli-responsive polymers and their applications Wei, Menglian; Gao, Yongfeng; Li, Xue Polymer Chemistry, Vol. 8, Issue 1 https://doi.org/10.1039/C6PY01585A	journal	January 2017
Stimuli-responsive smart gating membranes Liu, Zhuang; Wang, Wei; Xie, Rui Chemical Society Reviews, Vol. 45, Issue 3 https://doi.org/10.1039/C5CS00692A	journal	January 2016
Emerging applications of stimuli-responsive polymer materials Stuart, Martien A. Cohen; Huck, Wilhelm T. S.; Genzer, Jan Nature Materials, Vol. 9, Issue 2, p. 101-113 https://doi.org/10.1038/nmat2614	journal	January 2010
Biomimetic block copolymer particles with gated nanopores and ultrahigh protein sorption capacity Yu, Haizhou; Qiu, Xiaoyan; Nunes, Suzana P. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5110	journal	June 2014
Redox Cycling in Nanoscale-Recessed Ring-Disk Electrode Arrays for Enhanced Electrochemical Sensitivity Ma, Chaoxiong; Contento, Nicholas M.; Gibson, Larry R. ACS Nano, Vol. 7, Issue 6 https://doi.org/10.1021/nn401542x	journal	May 2013
Ion Accumulation and Migration Effects on Redox Cycling in Nanopore Electrode Arrays at Low Ionic Strength Ma, Chaoxiong; Xu, Wei; Wichert, William R. A. ACS Nano, Vol. 10, Issue 3 https://doi.org/10.1021/acsnano.6b00049	journal	February 2016
Ion selective redox cycling in zero-dimensional nanopore electrode arrays at low ionic strength Fu, Kaiyu; Han, Donghoon; Ma, Chaoxiong Nanoscale, Vol. 9, Issue 16 https://doi.org/10.1039/C7NR00206H	journal	January 2017
Nanochannel Arrays for Molecular Sieving and Electrochemical Analysis by Nanosphere Lithography Templated Graphoepitaxy of Block Copolymers Fu, Kaiyu; Bohn, Paul W. ACS Applied Materials & Interfaces, Vol. 9, Issue 29 https://doi.org/10.1021/acsami.7b06794	journal	July 2017
Asymmetric Nafion-Coated Nanopore Electrode Arrays as Redox-Cycling-Based Electrochemical Diodes Fu, Kaiyu; Han, Donghoon; Kwon, Seung-Ryong ACS Nano, Vol. 12, Issue 9 https://doi.org/10.1021/acsnano.8b03751	journal	August 2018
Redox Cycling in Individually Encapsulated Attoliter-Volume Nanopores Kwon, Seung-Ryong; Fu, Kaiyu; Han, Donghoon ACS Nano, Vol. 12, Issue 12 https://doi.org/10.1021/acsnano.8b08693	journal	November 2018
Nanoelectrodes, nanoelectrode arrays and their applications Arrigan, Damien W. M. The Analyst, Vol. 129, Issue 12, p. 1157-1165 https://doi.org/10.1039/b415395m	journal	January 2004
Ion Transport within High Electric Fields in Nanogap Electrochemical Cells Xiong, Jiewen; Chen, Qianjin; Edwards, Martin A. ACS Nano, Vol. 9, Issue 8 https://doi.org/10.1021/acsnano.5b03522	journal	July 2015
Redox Cycling in Nanogap Electrochemical Cells. The Role of Electrostatics in Determining the Cell Response Chen, Qianjin; McKelvey, Kim; Edwards, Martin A. The Journal of Physical Chemistry C, Vol. 120, Issue 31 https://doi.org/10.1021/acs.jpcc.6b05483	journal	July 2016
Fast Electron-Transfer Kinetics Probed in Nanofluidic Channels Zevenbergen, Marcel A. G.; Wolfrum, Bernhard L.; Goluch, Edgar D. Journal of the American Chemical Society, Vol. 131, Issue 32 https://doi.org/10.1021/ja902331u	journal	August 2009
Redox Cycling on Recessed Ring-Disk Nanoelectrode Arrays in the Absence of Supporting Electrolyte Ma, Chaoxiong; Contento, Nicholas M.; Bohn, Paul W. Journal of the American Chemical Society, Vol. 136, Issue 20 https://doi.org/10.1021/ja502052s	journal	May 2014
Engineered Asymmetric Heterogeneous Membrane: A Concentration-Gradient-Driven Energy Harvesting Device Zhang, Zhen; Kong, Xiang-Yu; Xiao, Kai Journal of the American Chemical Society, Vol. 137, Issue 46 https://doi.org/10.1021/jacs.5b09918	journal	November 2015
Highly ordered palladium nanodots and nanowires from switchable block copolymer thin films Bhoje Gowd, E.; Nandan, Bhanu; Vyas, Mukesh Kumar Nanotechnology, Vol. 20, Issue 41 https://doi.org/10.1088/0957-4484/20/41/415302	journal	September 2009
Ultrathin and Ion-Selective Janus Membranes for High-Performance Osmotic Energy Conversion Zhang, Zhen; Sui, Xin; Li, Pei Journal of the American Chemical Society, Vol. 139, Issue 26 https://doi.org/10.1021/jacs.7b02794	journal	June 2017
Supramolecular Assemblies from Poly(styrene)-block-poly(4-vinylpyridine) Diblock Copolymers Mixed with 6-Hydroxy-2-naphthoic Acid Bharatiya, Bhavesh; Schumers, Jean-Marc; Poggi, Elio Polymers, Vol. 5, Issue 2 https://doi.org/10.3390/polym5020679	journal	June 2013
Emulsion Solvent Evaporation-Induced Self-Assembly of Block Copolymers Containing pH-Sensitive Block Wu, Yuqing; Wang, Ke; Tan, Haiying Langmuir, Vol. 33, Issue 38 https://doi.org/10.1021/acs.langmuir.7b02330	journal	August 2017
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
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
Counterion Binding in Aqueous Solutions of Poly(vinylpyridines) as Assessed by Potentiometric Titration Roach, Jim D.; Bondaruk, Mandy M.; Al-Abdulghani, Abdulaziz Advances in Materials Physics and Chemistry, Vol. 06, Issue 09 https://doi.org/10.4236/ampc.2016.69025	journal	January 2016
The influence of cations on the electrode kinetics of ferricyanide-ferrocyanide system on the rotating gold electrode Kůta, Jaroslav; Yeager, Ernest Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 59, Issue 1 https://doi.org/10.1016/S0022-0728(75)80050-7	journal	February 1975
A microelectrode study of the mechanism and kinetics of the ferro/ferricyanide couple in aqueous media: The influence of the electrolyte and its concentration Beriet, C.; Pletcher, D. Journal of Electroanalytical Chemistry, Vol. 361, Issue 1-2 https://doi.org/10.1016/0022-0728(93)87042-T	journal	December 1993
pH-Sensitive nano-systems for drug delivery in cancer therapy Liu, Juan; Huang, Yuran; Kumar, Anil Biotechnology Advances, Vol. 32, Issue 4 https://doi.org/10.1016/j.biotechadv.2013.11.009	journal	July 2014
A Smart pH-responsive Nano-Carrier as a Drug Delivery System: A hybrid system comprised of mesoporous nanosilica MCM-41 (as a nano-container) & a pH-sensitive polymer (as smart reversible gatekeepers): Preparation, characterization and in vitro release studies of an anti-cancer drug Abbaszad Rafi, Abdolrahim; Mahkam, Mehrdad; Davaran, Soodabeh European Journal of Pharmaceutical Sciences, Vol. 93 https://doi.org/10.1016/j.ejps.2016.08.005	journal	October 2016
Iontronics: A Decade of Iontronic Delivery Devices (Adv. Mater. Technol. 5/2018) Arbring Sjöström, Theresia; Berggren, Magnus; Gabrielsson, Erik O. Advanced Materials Technologies, Vol. 3, Issue 5 https://doi.org/10.1002/admt.201870018	journal	May 2018
Iontronics Chun, Honggu; Chung, Taek Dong Annual Review of Analytical Chemistry, Vol. 8, Issue 1 https://doi.org/10.1146/annurev-anchem-071114-040202	journal	July 2015
Endeavor of Iontronics: From Fundamentals to Applications of Ion‐Controlled Electronics Bisri, Satria Zulkarnaen; Shimizu, Sunao; Nakano, Masaki Advanced Materials, Vol. 29, Issue 25 https://doi.org/10.1002/adma.201607054	journal	June 2017

Similar Records

Potential-induced wetting and dewetting in pH-responsive block copolymer membranes for mass transport control

Journal Article · Tue Dec 14 00:00:00 EST 2021 · Faraday Discussions · OSTI ID:1737368

Kwon, Seung-Ryong; Baek, Seol; Bohn, Paul W

Asymmetric Nafion-Coated Nanopore Electrode Arrays as Redox-Cycling-Based Electrochemical Diodes

Journal Article · Mon Aug 06 00:00:00 EDT 2018 · ACS Nano · OSTI ID:1737368

Fu, Kaiyu; Han, Donghoon; Kwon, Seung -Ryong; +1 more

Nanopore-enabled electrode arrays and ensembles

Journal Article · Tue Dec 29 00:00:00 EST 2015 · Mikrochimica Acta · OSTI ID:1737368

Zaino, Lawrence P.; Ma, Chaoxiong; Bohn, Paul W.

Related Subjects

77 NANOSCIENCE AND NANOTECHNOLOGY
36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Nanopore electrode arrays
block copolymers
redox cycling
ion channels
pH gates
permselectivity
redox reactions
electrodes
ions
membranes
nanopores

Title: Ion Gating in Nanopore Electrode Arrays with Hierarchically Organized pH-Responsive Block Copolymer Membranes

Citation Formats

References (53)

Similar Records

Related Subjects