Solid-Contact Ion-Selective and Reference Electrodes Covalently Attached to Functionalized Poly(ethylene terephthalate)
Solid-Contact Ion-Selective and Reference Electrodes Covalently Attached to Functionalized Poly(ethylene terephthalate)
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DOI：
10.1021/acs.analchem.0c00296
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发表时间：
2020-06-02
影响因子：
7.4
通讯作者：
Buhlmann, Philippe
中科院分区：
文献类型：
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作者：
Anderson, Evan L.;Chopade, Sujay A.;Buhlmann, Philippe
许多离子选择电极和参比电极已经发展了多年。随着对即时护理和可穿戴传感器的需求，最近的设计已经从具有水内填充溶液的笨重设备过渡到可平坦化的固体接触电极。然而，除非聚合物传感膜和参考膜被机械地固定在适当的位置，否则这些膜从它们粘附的底层固体中剥离会限制传感器的物理寿命。即使是很小的外部机械应力或热膨胀也会导致膜分层，从而导致设备故障。为了解决这个问题，我们设计了一个基于聚对苯二甲酸乙酯底物的传感平台，聚丙烯酸酯基传感膜和聚甲基丙烯酸酯基参考膜共价附着在该底物上。离子选择膜与共价连接或自由溶解的离子载体和离子液体掺杂的参考膜可以直接光聚合到表面功能化的聚对苯二甲酸乙酯上，导致底层底物和连接膜之间形成共价键。因此制备的H+-和K+选择性电极表现出具有理论预期（Nernstian）响应斜率的高选择性响应，参考电极在广泛的电解质浓度范围内提供与样品无关的参考电位。即使重复的机械应力也不会导致传感膜和参考膜的分层，从而使电极的长期性能得到很大改善。正如聚（乙烯-共环己烷-1,4-对苯二甲酸二甲酯）（PETG）所展示的那样，这种方法可以扩展到广泛的其他聚酯，聚酰胺和聚氨酯平台材料。传感膜和参考膜在惰性塑料平台材料上的共价附着是一种非常有前途的方法，解决了困扰离子选择电极和场效应晶体管领域30多年的问题。
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.