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

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

doi:10.1039/d1fd00048a

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

Journal Article · Mon Dec 13 23:00:00 EST 2021 · Faraday Discussions

DOI:https://doi.org/10.1039/d1fd00048a· OSTI ID:1978789

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Gyeongsang National University, Jinju (Korea, Republic of); OSTI
University of Notre Dame, IN (United States)

Wetting and dewetting behavior in channel-confined hydrophobic volumes is used in biological membranes to effect selective ion/molecular transport. Artificial biomimetic hydrophobic nanopores have been devised utilizing wetting and dewetting, however, tunable mass transport control utilizing multiple transport modes is required for applications such as controllable release/transport, water separation/purification and energy conversion. Here, we investigate the potential-induced wetting and dewetting behavior in a pH-responsive membrane composed of a polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) when fabricated as a hierarchically-organized sandwich structure on a nanopore electrode array (NEA), i.e. BCP@NEA. At pH < pK_a(P4VP) (pK_a ~ 4.8), the BCP acts as an anion-exchange membrane due to the hydrophilic, protonated P4VP cylindrical nanodomains, but at pH > pK_a(P4VP), the P4VP domains exhibit charge-neutral, hydrophobic and collapsed structures, blocking mass transport via the hydrophobic membrane. However, when originally prepared in a dewetted condition, mass transport in the BCP membrane may be switched on if sufficiently negative potentials are applied to the BCP@NEA architecture. When the hydrophobic BCP membrane is introduced on top of 2-electrode-embedded nanopore arrays, electrolyte solution in the nanopores is introduced, then isolated, by exploiting the potential-induced wetting and dewetting transitions in the BCP membrane. The potential-induced wetting/dewetting transition and the effect on cyclic voltammetry in the BCP@NEA structures is characterized as a function of the potential, pH and ionic strength. Additionally chronoamperometry and redox cycling experiments are used to further characterize the potential response. The multi-modal mass transport system proposed in this work will be useful for ultrasensitive sensing and single-molecule studies, which require long-time monitoring to explore reaction dynamics as well as molecular heterogeneity in nanoconfined volumes.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: FG02-07ER15851

OSTI ID:: 1978789

Alternate ID(s):: OSTI ID: 1835630

Journal Information:: Faraday Discussions, Journal Name: Faraday Discussions Journal Issue: 0 Vol. 233; ISSN 1359-6640

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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