Numerous ion-selective and reference electrodes have been developed over the years. Following the need for point-of-care and wearable sensors, designs have transitioned recently from bulky devices with an aqueous inner filling solution to planarizable solid-contact electrodes. However, unless the polymeric sensing and reference membranes are held in place mechanically, delamination of these membranes from the underlying solid to which they adhere physically limits sensor lifetime. Even minor external mechanical stress or thermal expansion can result in membrane delamination and, thereby, device failure. To address this problem, we designed a sensing platform based on poly(ethylene terephthalate) substrates to which polyacrylate-based sensing and polymethacrylate-based reference membranes are attached covalently. Ion-selective membranes with covalently attached or freely dissolved ionophore-and ionic-liquid-doped reference membranes can be directly photopolymerized onto surface-functionalized poly(ethylene terephthalate), resulting in the formation of covalent bonds between the underlying substrate and the attached membranes. H+-and K+-selective electrodes thus prepared exhibit highly selective responses with the theoretically expected (Nernstian) response slope, and reference electrodes provide sample-independent reference potentials over a wide range of electrolyte concentrations. Even repeated mechanical stress does not result in the delamination of the sensing and reference membranes, leading to electrodes with much improved long-Term performance. As demonstrated for poly(ethylene-co-cyclohexane-1,4-dimethanol terephthalate) (PETG), this approach may be expanded to a wide range of other polyester, polyamide, and polyurethane platform materials. Covalent attachment of sensing and reference membranes to an inert plastic platform material is a very promising approach to a problem that has plagued the field of ion-selective electrodes and field effect transistors for over 30 years.
Bibliographical noteFunding Information:
E.L.A. thankfully acknowledges a Lester C. and Joan M. Krogh Endowed Fellowship, an ACS Division of Analytical Chemistry and Eastman Summer Fellowship, a Richard D. Amelar and Arthur S. Lodge Fellowship, and a Dissertation Fellowship from the Graduate School, University of Minnesota. The support of the National Science Foundation through Award DMR-1707578 (T.P.L.), DMR-1609459 and DMR-2003454 (M.A.H.), and CHE-1710024 (P.B.) is appreciated. The authors thank Lisa Zeeb for the help preparing Figure 2.
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PubMed: MeSH publication types
- Journal Article
- Research Support, Non-U.S. Gov't
- Research Support, U.S. Gov't, Non-P.H.S.