Tailoring Conducting Polymer Interface for Sensing and Biosensing

Abstract: The routine measurement of significant physiological and biochemical parameters has become increasingly important for health monitoring especially in the cases of elderly people, infants, patients with chronic diseases, athletes and soldiers etc. Monitoring is used to assess both physical fitness level and for disease diagnosis and treatment. Considerable attention has been paid to electrochemical sensors and biosensors as point-of-care diagnostic devices for healthcare management because of their fast response, low-cost, high specificity and ease of operation. The analytical performance of such devices is significantly driven by the high-quality sensing interface, involving signal transduction at the transducer interface and efficient coupling of biomolecules at the transducer bio-interface for specific analyte recognition. The discovery of functional and structured materials, such as metallic and carbon nanomaterials (e.g. gold and graphene), has facilitated the construction of high-performance transducer interfaces which benefit from their unique physicochemical properties. Further exploration of advanced materials remains highly attractive to achieve well-designed and tailored interfaces for electrochemical sensing and biosensing driven by the emerging needs and demands of the “Internet of Things” and wearable sensors.Conducting polymers (CPs) are emerging functional polymers with extraordinary redox reversibility, electronic/ionic conductivity and mechanical properties, and show considerable potential as a transducer material in sensing and biosensing. While the intrinsic electrocatalytic property of the CPs is limited, especially for the bulk polymer, tailoring of CPs with controlled structure and efficient dopants could improve the electrochemical performance of a transducer interface by delivering a larger surface area and enhanced electrocatalytic property. In addition, the rich synthetic chemistry of CPs endows them with versatile functional groups to modulate the interfacial properties of the polymer for effective biomolecule coupling, thus bridging organic electronics and bioelectrochemistry. Moreover, the soft-material characteristics of CPs enable their use for the development of flexible and wearable sensing platforms which are inexpensive and light-weight, compared to conventional rigid materials, such as carbons, metals and semiconductors.This thesis focuses on the exploration of CPs for electrochemical sensing and biosensing with improved sensitivity, selectivity and stability by tailoring CP interfaces at different levels, including the CP-based transduction interface, CP-based bio-interface and CP-based device interface.First, we demonstrate different strategies for tailoring the physicochemical properties of poly (3,4-ethylenedioxythiophene) (PEDOT) beyond its intrinsic properties, via charge effects, structural effects and by the use of hybrid materials, as a CP-based transduction interface to improve sensing performance of various analytes. 1) A positively-charged PEDOT interface, and a negatively-charged carboxylic-acid-functionalised PEDOT (PEDOT:COOH) interface were developed to modulate the electrode kinetics for oppositely-charged analytes, e.g. negatively-charged nicotinamide adenine dinucleotide (NADH) and positively-charged dopamine (DA), respectively. These interfaces displayed high sensitivity and wide linear range towards the analytes due to the electrostatic attraction effect. 2) Various structured PEDOT including porous microspheres and nanofibres were synthesised via hard-template and soft-template methods, respectively, and were employed as building blocks for a hierarchical PEDOT and 3D nanofibrous PEDOT transduction interface, that facilitated signal transduction for NADH. 3) A PEDOT hybrid material interface was developed via using a novel bi-functional graphene oxide derivative with high reduction degree and negatively-charged sulphonate terminal functionality (S-RGO) as dopant to create PEDOT:S-RGO which delivered an enhanced electrochemical performance for various analytes.Based on the established CP-based transduction interface, biomolecules (e.g. enzymes) could be coupled to the CP surface to create CP-based bio-interfaces for biosensing. The immobilisation of enzyme was realised via either covalent bonding to a PEDOT derivative bearing a -COOH group (PEDOT-COOH) through EDC/NHS chemistry, or by physical absorption into the 3D porous PEDOT structure. The CP-based bio-interfaces were used to demonstrate the stable immobilisation of two different types of enzymes, i.e. lactate dehydrogenase and lactate oxidase, achieving the biosensing of analytes by relay bioelectrochemical signal transduction.Together, CP was employed as the CP-based device interface for the fabrication of a flexible and wearable biosensing device. A 3D honeycomb-structured graphene network was generated in-situ on a flexible polyimide surface by mask-free patterning using laser irradiation. The substrate was then reinforced with PEDOT as a polymeric binder to stabilise the 3D porous network by adhesion and binding, thus minimising the delamination of the biosensing interface under deformation and enhancing the mechanical behaviours for use in flexible and wearable devices. The subsequent nanoscale-coating of Prussian blue and immobilisation of enzyme into the 3D porous network provided a flexible platform for wearable electrochemical biosensors to detect lactate in sweat.