Disulfide Incorporated Pyridine and Pyridinium Push-Pull Dyes for Optical Sensing and Antifouling Electrodes

Andrew R. Brotherton; Naedum DomNwachukwu; Matthew D. Bailey; Jonathan Rivnay; Thomas J. Meade

doi:10.1021/acs.langmuir.4c04953

Disulfide Incorporated Pyridine and Pyridinium Push-Pull Dyes for Optical Sensing and Antifouling Electrodes

Andrew R. Brotherton, Naedum DomNwachukwu, Matthew D. Bailey, Jonathan Rivnay, Thomas J. Meade^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

A new push-pull dye has been developed as a pH indicator when covalently copolymerized in a lipoic acid-based polymer (LA-Py). Furthermore, various charged forms of the dyes are investigated as antifouling diluents in self-assembled monolayers (SAMs) on gold electrodes. The dyes contain an amino donor incorporated into a seven-membered heterocyclic disulfide ring, a pyridine or pyridinium acceptor moiety, and an oligo-phenylene ethylene (OPE) conjugated bridge. A common characteristic of a push-pull dye is the high sensitivity to solvent dipoles such as the Stokes shifts of 176 and 211 nm for pyridine (Py) in acetonitrile and pyridinium (MePy) in chloroform, respectively. This is coupled with a decrease in quantum yields with increasing polarity of the solvents. The LA-Py has an apparent pK_a of 3.5 and showed high sensitivity in acidic conditions with robust cycling between pH 7 and −0.08, producing an average contrast of 36% over 10 cycles. Incorporated into a SAM, the zwitterionic pyridinium sulfonate (SPy) derivative demonstrated antifouling to BSA by continuous monitoring of impedance with electrochemical impedance spectroscopy and ionic permeability of K₃[FeCN₆] by cyclic voltammetry. When “backfilled” with mercaptohexadecane (MHD), an enhanced SAM was formed (SPy + MHD), which showed resistance to ion penetration and improved antifouling.

Original language	English (US)
Pages (from-to)	8144-8151
Number of pages	8
Journal	Langmuir
Volume	41
Issue number	12
DOIs	https://doi.org/10.1021/acs.langmuir.4c04953
State	Published - Apr 1 2025

Funding

A.R.B. gratefully acknowledges the NSF Graduate Research Fellowship Grant no. DGE-2234667. This research is sponsored by the Defense Advanced Research Projects Agency (DARPA) through Cooperative Agreement D20AC00002 awarded by the U.S. Department of the Interior (DOI), Interior Business Center. The content of the information does not necessarily reflect the position or the policy of the Government, and no official endorsement should be inferred. This work made use of the IMSERC MS facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), the State of Illinois, and the International Institute for Nanotechnology (IIN). This work made use of the NUFAB facility of Northwestern University\u2019s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern\u2019s MRSEC program (NSF DMR-2308691).

ASJC Scopus subject areas

General Materials Science
Condensed Matter Physics
Surfaces and Interfaces
Spectroscopy
Electrochemistry

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10.1021/acs.langmuir.4c04953

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title = "Disulfide Incorporated Pyridine and Pyridinium Push-Pull Dyes for Optical Sensing and Antifouling Electrodes",

abstract = "A new push-pull dye has been developed as a pH indicator when covalently copolymerized in a lipoic acid-based polymer (LA-Py). Furthermore, various charged forms of the dyes are investigated as antifouling diluents in self-assembled monolayers (SAMs) on gold electrodes. The dyes contain an amino donor incorporated into a seven-membered heterocyclic disulfide ring, a pyridine or pyridinium acceptor moiety, and an oligo-phenylene ethylene (OPE) conjugated bridge. A common characteristic of a push-pull dye is the high sensitivity to solvent dipoles such as the Stokes shifts of 176 and 211 nm for pyridine (Py) in acetonitrile and pyridinium (MePy) in chloroform, respectively. This is coupled with a decrease in quantum yields with increasing polarity of the solvents. The LA-Py has an apparent pKa of 3.5 and showed high sensitivity in acidic conditions with robust cycling between pH 7 and −0.08, producing an average contrast of 36% over 10 cycles. Incorporated into a SAM, the zwitterionic pyridinium sulfonate (SPy) derivative demonstrated antifouling to BSA by continuous monitoring of impedance with electrochemical impedance spectroscopy and ionic permeability of K3[FeCN6] by cyclic voltammetry. When “backfilled” with mercaptohexadecane (MHD), an enhanced SAM was formed (SPy + MHD), which showed resistance to ion penetration and improved antifouling.",

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AB - A new push-pull dye has been developed as a pH indicator when covalently copolymerized in a lipoic acid-based polymer (LA-Py). Furthermore, various charged forms of the dyes are investigated as antifouling diluents in self-assembled monolayers (SAMs) on gold electrodes. The dyes contain an amino donor incorporated into a seven-membered heterocyclic disulfide ring, a pyridine or pyridinium acceptor moiety, and an oligo-phenylene ethylene (OPE) conjugated bridge. A common characteristic of a push-pull dye is the high sensitivity to solvent dipoles such as the Stokes shifts of 176 and 211 nm for pyridine (Py) in acetonitrile and pyridinium (MePy) in chloroform, respectively. This is coupled with a decrease in quantum yields with increasing polarity of the solvents. The LA-Py has an apparent pKa of 3.5 and showed high sensitivity in acidic conditions with robust cycling between pH 7 and −0.08, producing an average contrast of 36% over 10 cycles. Incorporated into a SAM, the zwitterionic pyridinium sulfonate (SPy) derivative demonstrated antifouling to BSA by continuous monitoring of impedance with electrochemical impedance spectroscopy and ionic permeability of K3[FeCN6] by cyclic voltammetry. When “backfilled” with mercaptohexadecane (MHD), an enhanced SAM was formed (SPy + MHD), which showed resistance to ion penetration and improved antifouling.

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Disulfide Incorporated Pyridine and Pyridinium Push-Pull Dyes for Optical Sensing and Antifouling Electrodes

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