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PEDOT) Derivatives: Innovative Conductive Polymers for Bioelectronics

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PEDOT) Derivatives: Innovative Conductive Polymers for Bioelectronics polymers Review Poly(3,4-ethylenedioxythiophene) (PEDOT) Derivatives: Innovative Conductive Polymers for Bioelectronics Daniele Mantione 1,†, Isabel del Agua 1,2,†, Ana Sanchez-Sanchez 1,2,* and David Mecerreyes 1,3,* 1 Polymat University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avda. Tolosa 72, 20018 Donostia-San Sebastian, Spain; [email protected] (D.M.); [email protected] (I.d.A.) 2 Department of Bioelectronics, Ecole Nationale Supérieure des Mines, CMP-EMSE, MOC, 13541 Gardanne, France 3 Ikerbasque, Basque Foundation for Science, E-48011 Bilbao, Spain * Correspondence: [email protected] (A.S.-S.); [email protected] (D.M.); Tel.: +34-943-015-323 (A.S.-S.); +34-943-018-018 (D.M.) † These authors contributed equally. Received: 26 June 2017; Accepted: 8 August 2017; Published: 11 August 2017 Abstract: Poly(3,4-ethylenedioxythiophene)s are the conducting polymers (CP) with the biggest prospects in the field of bioelectronics due to their combination of characteristics (conductivity, stability, transparency and biocompatibility). The gold standard material is the commercially available poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). However, in order to well connect the two fields of biology and electronics, PEDOT:PSS presents some limitations associated with its low (bio)functionality. In this review, we provide an insight into the synthesis and applications of innovative poly(ethylenedioxythiophene)-type materials for bioelectronics. First, we present a detailed analysis of the different synthetic routes to (bio)functional dioxythiophene monomer/polymer derivatives. Second, we focus on the preparation of PEDOT dispersions using different biopolymers and biomolecules as dopants and stabilizers. To finish, we review the applications of innovative PEDOT-type materials such as biocompatible conducting polymer layers, conducting hydrogels, biosensors, selective detachment of cells, scaffolds for tissue engineering, electrodes for electrophysiology, implantable electrodes, stimulation of neuronal cells or pan-bio electronics. Keywords: PEDOT; conducting polymers; biopolymers; bioelectronics 1. Introduction Electrically conductive polymers are of great interest in the field of bioelectronics as materials that can improve the interface between electronics and biology. Among different conducting polymers, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is the most promising due to its high conductivity, easy processing and commercial availability [1,2]. PEDOT:PSS is commercialized in the form of an aqueous dispersion which can be processed in the form of thin films by spin-coating and solvent-casting methods. PEDOT:PSS is widely used in the field of organic electronics as transparent conductive oxides (TCO), and as a hole-conducting layer or electrochromic layer in a variety of devices from organic light-emitting diodes (OLEDs) and organic photovoltaic devices (OPVs) [3,4] to electrochromics [5,6]. In recent years, PEDOT:PSS has also been widely applied in bioelectronic devices for applications as electrodes for electrophysiology, a variety of biosensors, organic electrochemical transistors (OECTs) and small bioelectrode coatings [6–15]. However, in order to connect well the two fields of biology and electronics, PEDOT:PSS presents some limitations, mostly due to its low biofunctionality and biocompatibility. Polymers 2017, 9, 354; doi:10.3390/polym9080354 www.mdpi.com/journal/polymers Polymers 2017, 9, 354 2 of 21 In most bioelectronic applications, the fine tuning of the interface of conducting polymers and biological molecules or tissues/organisms is a crucial parameter. As one illustrative example, the biotic/abiotic interface for interfacing with live cells can be improved by the incorporation of biological molecules such as nucleotides or proteins for functionality, e.g., for sensing. In this way, the biofunctionalized conductive polymer can enhance their ultimate properties such as biocompatibility and adhesion, and could help to reduce the inflammatory response of a device in living tissue. The two components of PEDOT:PSS are limited, due on the one hand to the lack of functionality of PEDOT andPolymers on the 2017 other, 9, x FOR hand PEER to theREVIEW low biocompatibility of PSS. To overcome these limitations, much effort2 of 23 has been devoted to design innovative poly(dioxythiophene) polymers containing different functional groupselectronics for improved, PEDOT:PSS biocompatibility presents some [16, 17limitations]. , mostly due to its low biofunctionality and biocompatibility.In this review, we summarize recent advances in the design of innovative conductingIn most polydioxythiophenebioelectronic applications (PEDOT, the fine poly(3,4-ethylenedioxythiophene)tuning of the interface of conducting or polymers ProDOT and poly(3,4-Propylenedioxythiophene))-typebiological molecules or tissues/organisms materials is a crucial for parameter. bioelectronics As one (Figure illustrative1). The example, broadest the usedbiotic/abiotic material todayinterface is the for commercially interfacing with available live cells poly(3,4-ethylenedioxythiophene):poly(styrene can be improved by the incorporation of sulfonate)biological (PEDOT:PSS) molecules such aqueous as nucleotides dispersion or which proteins has twofor functionality, main components: e.g., for PEDOT sensing. and In PSS. this First, way, wethe focus biofunctionalized our efforts on discussing conductive the differentpolymer synthetic can enhance routes totheir modify ultimate the first propert componenties PEDOT.such as Thus,biocompatibility we will review and the adhesion different, and functional could EDOThelp to and reduce ProDOT the inflammatory monomers and response their derivatives of a device that in haveliving been tissue. reported The intwo the components scientific literature. of PEDOT:PSS Next, we are review limited the, differentdue on the trials one to hand substitute to the PSS, lack the of secondfunctionality component of PEDOT of the material.and on the Here, other we hand review to the low synthesis biocompatibility of PEDOT:biopolymer of PSS. To aqueousovercome dispersions.these limitations, Finally, wemuch discuss effort how has these been innovative devoted functionalto design PEDOT innovative materials poly(dioxythiophene) are widening the scopepolymers of the containing applications different of conducting functional polymers groups infor bioelectronics. improved biocompatibility [16,17]. Monomer functionalization PSS substitution by Biopolymers Applications in Bioelectronics FigureFigure 1. 1.Graphical Graphical representation representation of of alternative alternative materials materials to to PEDOT:PSS PEDOT:PSS described described in in this this review. review. 2. SynthesisIn this of review, Functional we Ethylenedioxythiophenesummarize recent advances (EDOT-ProDOT) in the design Monomers of innovative conducting polydioxythiophene (PEDOT poly(3,4-ethylenedioxythiophene) or ProDOT poly(3,4There-Propylenedioxythiophene)) are two main different methods-type materials to synthesize for bioelectronics functional 3,4-ethylenedioxothiophene(Figure 1). The broadest used monomers.material today One syntheticis the routecommercially involves theavailable creation poly(3,4 of the thiophene-ethylenedioxythiophene): and dioxolane derivativespoly(styrene (Figuresulfonate)2 pathway (PEDOT:PSS) #1). In aqueous the second dispersion synthetic which route, has the two starting main components material is a: PEDOT 3,4-substituted and PSS. thiopheneFirst, we focus ring, forour exampleefforts on 3,4-dimethoxythiophene discussing the different synthetic or 3,4-dibromothiophene routes to modify (Figurethe first2 componentpathway #2).PEDOT. The macroscopic Thus, we will difference review betweenthe different the twofunctional synthetic EDOT routes and is theProDOT number monomers of steps toand reach their thederivatives final product: that have in the been case reported of pathway in the #1,scientific more stepsliterature. are needed, Next, we but review the price the different of the starting trials to materialsubstitute for pathwayPSS, the #2second is about component 10 to 100 timesof the more material. expensive Here than, we for review pathway the #1. synthesis It is worth of mentioningPEDOT:biopolymer that pathway aqueous #1 is the dispersions. oldest synthetic Finally, route we and discuss has only how been these employed innovative for the synthesisfunctional ofPEDOT 2-hydroxymethyl-EDOT materials are widening (EDOT-CH the2OH) scope and carboxy-EDOTof the applications (EDOT-COOH) of conducti [13,16ng]. Inpolymers the case ofin EDOT-CHbioelectronics.2OH following pathway #2, the reaction with glycerol tends to yield a mixture of EDOT and ProDOT that is difficult to separate. In the case of EDOT-COOH, PCC (pyridinium chlorochromate) is used2. Synthesis in an oxidative of Functional step and Ethylenedioxythiophene the groups in position 2 and (EDOT 5 on the-ProDOT) thiophene Monom ring protecters the molecule from further polymerization when pathway #1 is used [13]. For the ProDOT derivatives, pathway #2 is There are two main different methods to synthesize functional 3,4-ethylenedioxothiophene the only route used in the literature, whereby 1,3-diol derivatives are used to create the dioxepane ring. monomers. One synthetic route involves the creation of the thiophene and dioxolane derivatives (Figure 2 pathway #1). In the second synthetic route, the starting material is a 3,4-substituted thiophene
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