Pedot 1

Synthetic Metals 273 (2021) 116709
Contents lists available at ScienceDirect
Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet
PEDOT and PEDOT:PSS conducting polymeric hydrogels: A report on their

emerging applications
Mushtaq A. Bhat, Reyaz A. Rather, Aabid H. Shalla *
Department of Chemistry, School of Sciences, Islamic University of Science and Technology, Awantipora 192122, India
A R T I C L E I N F O A B S T R A C T
Keywords: Conducting polymers (CP’s) are currently being explored in areas like bio-interfaces, bioelectronics and medical
PEDOT purposes. Inclusion of moieties of CP’s into hydrogels has received substantial traction in recent years due to
Conducting hydrogels their high conduction (both electrical and electrolyte phases), adjustable mechanical properties, swelling
Bioelectronics
disposition and their tunable three dimensional (3D) matrix. As such conducting polymeric hydrogels (CPH’s)
Conducting polymers
have successfully emerged as potential candidates for medical therapies, medical and bioelectronics, environ
mental pollution treatments, energy storage and sensors. CPH’s provide a better platform for envisaging inno
vative technologies including flexible electronic devices like supercapacitors due to the flexible nature of CPH’s.
Among large class of CP’s poly (3,4-ethylenedioxythiophene) (PEDOT) has attracted huge interest in fabrication
of CPH’s. PEDOT has emerged as a champion material in field of bioelectronics harboring broader domain of
applications with an added advantage related to its versatile synthetic process. PEDOT in combination with
Polystyrene sulfonate (PSS) (as CPH’s) shows strong potential in bioelectronics due to its high stability main
taining the redox coloration and electrical conductivity (1–10 S cm-1) of PEDOT itself and hence tuning the
conducting nature of PEDOT:PSS based hydrogels is very interesting area to explore. We take this opportunity to
describe chemical forms and functionalities of PEDOT based CPH’s. Finally we review PEDOT based CPH’s and
enlist the applications of PEDOT based CPH’s in 3D patterning, bioelectronics, tissue engineering, drug delivery
and electrode purposes.
1. Introduction 1.1. Importance of CP’s
Hydrogels are multidimensional polymeric systems displaying hy CP’s are noble prize winning organic materials and have attracted
drophilic characteristics, obtained from natural or synthetic polymers massive attention due to their exceptional electro-optical properties
and sustain themselves in water due to various crosslinking mechanisms resembling directly to conventional inorganic semiconductors and
[1]. Their wider scope is usually imparted due to their unique resem metals. The synthesis of CP’s can be carried out using simple, versatile,
blance with extracellular matrix, their biocompatibility, functionality and cost-effective approaches with easy tunability of their functional
and adjustable mechanical and biochemical properties [2,3] and these ities [14–16]. They display the property of self-assembled supramolec
unique properties have been explored in fields like environmental [4–6], ular architectures with retention of high functionality en-route
biomedical [7,8], antibacterial [9], wound-healing [10,11], metal electro-polymerization methods [17]. These properties originate from
remediation applications [12] etc. However their use in tissue scaffolds conjugated nature of their backbones and to subsequent display of
like: neural tissues, cardiac tissue, and skeletal muscle tissues are limited polaron and bipolaron structure representing singly and doubly charged
due to their non-conducting nature [13]. We will conscript the use of quasiparticles. Use of Carbon nanotubes (CNTs), Carbon nanowires
CP’s like Poly (3,4-ethylenedioxythiophene) (PEDOT) and Polyaniline in (CNWs), Graphene oxide (GO) and metallic particles are also used as
our review that modulate the conductivity, mechanical and biochemical conducting materials, however the effective and extensive use of such
properties of hydrogels in biomedical fields. However our review will be systems is limited due to their non-biodegradability, inconclusive evi
more focused over PEDOT based systems. dence of in-vivo toxicity and anisotropically distributed conducting
particles in composite systems [18–21]. Conducting polymers such as
* Corresponding author.
E-mail address: [email protected] (A.H. Shalla).
https://doi.org/10.1016/j.synthmet.2021.116709
Received 12 October 2020; Received in revised form 19 December 2020; Accepted 12 January 2021
Available online 1 February 2021
0379-6779/© 2021 Elsevier B.V. All rights reserved.
M.A. Bhat et al. Synthetic Metals 273 (2021) 116709
Polypyrrole (PPy), Polyaniline (PANI), PEDOT etc. have been well mechanical attributes, swelling disposition, porosity and degradability
investigated. What is more the CP’s display a tremendous potential for need to be looked into due to their direct effect on in vivo tissue
achieving control over number of cellular functions such as cell adhe regeneration [43,44]. Biocompatibility of CPH’s is a requirement in
sion, proliferation, relocation and differentiation of neural and muscle different applications [45] and CPH’s-containing PEDOT, PANI have
cells [22–25]. These polymers display suitability for applications in been investigated in large number of applications with detailed inves
energy and bioelectronics in form of several devices such as super tigation on biocomaptibility of such polymers. Injectable PANI hydro
capacitors, electrochemical sensors, drug delivery systems, and organic gels based on dextran crosslinked gelatin-graft-polyaniline and
transistors, flexible energy storage, touch panel, biosensors, neural carboxymethyl-chitosan reported by Guo and coworkers [46] have
prostheses [26–28] (Fig. 1) (OFETs and OECTs). Further the control over shown good cyto-compatibility tests with adipose-derived mesenchymal
the designing of polymer morphology in the nanometer range could be stem cells showing significant enhancement in the growth of C2C12
an added advantage to produce new functional materials. myoblasts. The biocompatibility at subcutaneous levels was studied
One of the best and most important among conducting polymers is using foreign body response while carried out subcutaneous implanta
PEDOT that harbors its application domain in multiple number of fields tion in Sprague Dawley rats. The presence of little fibrous tissue casing
including energy storage and conversion, bioelectronics, solar-cells, around the hydrogels after 1 and 4 weeks showed their good biocom
sensing and electrochemical devices [29]. In recent years such systems patibility. Thus the results revealed the strong nature of PANI conduc
like PPy, PANI, and PEDOT etc. have been investigated on variety of tive hydrogels as excellent candidates for biomedical applications. Some
hydrogel materials in which the polymer support is provided by poly of the applications of PANI based hydrogels are highlighted in Table1
mers such as polyacrylamide, poly (acrylic acid) or many available [47–68]. The present aspect of CPH’s offers a huge prospects in different
biopolymers such as gelatin, chitosan, cellulose etc. [30,31]. areas as is highlighted for PEDOT hydrogels in Table 2 [69–85] showing
their important application prospects in different fields.
1.2. Importance of CPH’s The CPH’s offer tunability in their properties via controlling the
proportion of CP and hydrogel materials. For designing CPH’s the most
CPH’s are smart in nature, an amalgam of characters both of important consideration is selection of polymers with high carrier
hydrogels as well as conducting polymers, by promoting a better inter mobility and high overall conductance, mechanical stability and envi
face between electronic conducting (electrode) and the ionic-conducting ronmental stimuli responsive nature. For example skin tissue is also
phases (electrolyte). They display multidimensional characteristics such conducting in nature (2.6 mS cm-1 to 1 × 10–4 mS cm-1), and is sensitive
as transport phenomenon of charges, ions and molecules due to the to electrical effects thus material possessing novel functionalities may
intrinsic 3D microstructure in a conducting framework. Thus the most prove better wound dressing material in encouraging wound regenera
intrinsic characteristic of CPH’s is the combination in the same material tion process. Therefore, different ideas and approaches have been
in which the electro-activity is given by the conducting polymer and the designed and used simultaneously to manage and restore the overall
ionic conductivity given by the aqueous media [32]. They share a close properties of CPH’s, which generally includes the insertion of underly
relationship between natural and biological tissues and between soft and ing polymers, components considered highly bioactive, and
hard materials [33]. They are easily processable and molded into thin
films with any shape at gelation point. Further their major advantage is Table 1
micro-patterning through ink jet that helps to achieve any design and PANI based hydrogels and their applications.
also with self –healing, biocompatibility and self-adhesive properties in
Supporting polymer or material Applications Ref.
them [34–38]. CPH’s are valued customers for tissue engineered appli
cations such as tissue scaffolds and electro-responsive modulation of Carboxymethyl cellulose–PANI (CMC–PANI) Antimicrobial [47]
application
different cells including neurons, cardiac tissue cells endothelial cells, polyaniline– polythionine redox hydrogel Immunosensor toward [48]
and mesenchymal stem cells (MSCs) [39–42]. The challenges in tissue carcinoma antigen-125
engineering regarding the physical properties of CPH’s including their PAA, RGO, vinyl substituted polyaniline (VS- Glucose Sensor [49]
PANI) and lutetium Phthalocyanine (LuPc2)
PAM–PVA–PANI Urea Electrochemical [50]
biosensor
polyaniline–poly(styrene sulfonate) (PANI–PSS) Urea biosensor [51]
Polyaniline-poly (styrene sulfonate) hydrogels. H2O2 sensor [52]
(PAA)–PANI Tissue engineering [53]
PANI and graphene-poly(e-caprolactone) (PCL) Tissue engineering [54]
PANI–cellulose phytic acid Neural repairing [55]
PANI with L-glutamic acid(GA) Drug delivery [56]
PAM–itaconic acid–PANI (PAAm–IA–PANI) Drug delivery [57]
Poly(isopropyl acrylamide-co-acrylic acid)– Actuators applications [58]
PAA–PANI (PNIPAM–PAA–PANI)
PVA–PANI Supercapacitor [59]
applications
Si–PANI–graphene Supercapacitor [60]
applications
PANI-reduced graphene oxide hydrogel Supercapacitor [61]
(PANI–RGOHG) applications
CMC–PAA–PANI Supercapacitor [62]
applications
Self-crosslinked polyaniline hydrogel Supercapacitor [63]
applications
PAA–polyphenylenediamine–PANI Capacitance [64]
(PAA–PPDA–PANI)
GO and poly(2-acrylamide-2-methyl-1- Supercapacitor [65]
propanesulfonic acid) (denoted as applications
PANI–PAMPA)-based conducting hydrogel
Fig. 1. Conducting Hydrogel desirable applications. PAA–PEG–PANI Solar cells [66]
PAA–CTAB–PANI Solar cells [67]
Preprinted (Adapted) with permission from (Chemistry a European Journal 24
poly(Nvinyl-2-pyrrolidone)–PANI pH sensitivity [68]
(2018) 16930–16943) Copyright (2018) Wiley online Library.
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Table 2 1.3. Synthetic methods of CPH’s

Applications of PEDOT and PEDOT:PSS based CPH’s.
Supporting/Polymer or material Application Ref. Hybrid polymers obtained from conducting polymers and hydrogels
poses many challenges in terms of their production pertaining to the
PEDOT:PSS/H2SO4 Supercapacitor [69]
PEDOT:PSS/DMSO 3D printing [70] dissimilar starting materials employed in their preparation process.
PEDOT-PVA/Na2SO4 Supercapacitor [71] There are three general established routes in order to frame conducting
PNAGA-PAMPS/PEDOT:PSS Supercapacitor/Tissue Engineering [72] hydrogels (Fig. 2(a)–(c)) [89].
Scaffolds
PEDOT-γ-PGA Energy storage [73]
PEDOT:PSS/EMIM:ES(IL) 3D micro-patterning patterning [74]
1.3.1. Method 1
PEDOT-Phytic acid-PANI Solid state capacitor [75] This method is also called as template method where desired pattern
PEDOT Modified Pt electrode/ Micro-patterning [76] is achieved by removable template material and then CP monomer is
Agarose polymerized in template pattern. The hydrogel-template method is most
PEDOT:PSS/ GeIMA Tissue Engineering [77]
commonly used method as shown in (Fig. 2(a)). The initial process starts
PEDOT-Xanthan Gum Tissue Engineering [78]
PEDOT-COOH Tissue Engineering [79] with synthesis of hydrogel template followed by dehydration and is then
PEDOT-PEG Myoblast Differentiation/ Tissue [80] allowed for in-situ polymerization in presence of CP monomers by either
Engineering electrochemical polymerization or by adding chemical oxidants. This
PEDOT: Sulphonated lignin Bioelectronics [81] synthetic route has been applied for number of CPH’s such as PANI or
PEDOT-PSS-Peptide PEG Tissue Engineering [82]
PEDOT: SL-ALG-ADM- Tissue Engineering [83]
PPy–PNIPAM, [90] PEDOT–alginate, [70,91] PEDOT–PAA (polyacrylic
Cyclodextrin acid), [92] and PPy–PAAm (polyacrylamide) [93] and have been suc
PDMAAp/PEDOT Drug Delivery [84] cessfully synthesized via this strategy. However, the limited scalability
PEDOT-Alginate Drug Delivery [85] of template-guided synthesis inhibits its further application. For
example use of multivalent metal ions (Fe3+ or Mg2+) to crosslink poly
functionalities with dual characteristics, and finally the nature and (3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) [94,
amount of crosslinking within the polymeric networks [86–88]. Thus it 95] and similarly using poly(ethylene glycol) diglycidyl ether
becomes important to review the overall capacity modulation of (non-conducting polymer), or poly(styrenesulfonate) to crosslink PANI
hydrogels in presence PEDOT as champion material and their huge [95,96]. However the electrical properties of these CPH’s compromised
application window. due to use of non-conducting hydrogel matrix and polymers. Further
Fig. 2. Schematic illustration of some general routes of CPH synthesis (a) Template method (b) CPH synthesis involves deswelling process followed by swelling in CP
solution to its original volume. The re-swollen hydrogel is allowed to polymerize (CP polymerization) in an oxidative initiator and dopant mixtures. The images show
different stages of CPH formation (c) Showing CPH’s formed by mixing polymer precursors either simultaneously or carried in a two-step process.
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excessive use of metal ions adapted in the polymerization process re first synthetic report in the year 1988 [116]. PEDOT is potentially
duces the biocompatibility of hydrogels hence limits their potential applicable in number of fields like energy storage and conversion, bio
scalability. electronics, photovoltaics, sensing and electrochemical devices, such as
electrochemical transistors [25]. It is stable to air and moisture
1.3.2. Method 2 compared to other reported conducting polymers, such as polyaniline,
In this route initially hydrogels are dehydrated and they subse polyacetylene and polypyrrole and is also chemically and thermally
quently allowed to swell in CP monomer solution with polymerization of stable [117]. It has the advantages of biocompatibility, [117] a
CP monomer. The representative examples in this case are Poly(acrylic competitive theoretical specific capacitance of 210 Fg-1 with high con
acid) (PAA)-PEDOT [97] Poly(2-acrylamido-2-methylpropanesulfonic ductivity (up to 4500 S cm-1) [118–121] and can be operated under a
acid) (PAMPS)-PANI hydrogels [98]. larger voltage window than most other CP’s [122]. Among the various
A supporting hydrogel polymer finally forms a matrix for the available polymerization methods the most common is oxidative poly
hydrogel synthesis [99]. The procedure of the method is shown in (Fig. 2 merization method. The polymerization is carried from its monomer 3,
(b)). CPH consist of CP formed in water soluble polymer, which shows 4-ethylenedioxythiophene (EDOT). Oxidized forms of PEDOT with
swelling properties with water or electrolyte solution. Initially a positive charges are usually stabilized by counterions such as perchlo
hydrogel matrix is formed by de-swelling process and final the matrix is rate (ClO−4 ), and polystyrene sulfonate (PSS) (Fig. 3(b)) [123]. The
allowed to swell in CP solution. This matrix containing CP monomers is methodology of film formation may be achieved through two different
allowed to polymerize in an oxidant solution, initially diffused into the routes.
matrix, leading to polymerization of CP monomers. This method is One method involves in-situ polymerization i.e. synthesis of PEDOT
known as interfacial polymerization and is utilized for achieving CPHs itself during the film formation of PEDOT:tosylate (tos) with conduc
where PANI [100–102] PPy [103–107] and rarely PEDOT [108–112] tivity values reported upto 4300 S cm-1 [118]. The other polymerization
are taken as conducting polymers. Interfacial methods have been methods of PEDOT involves film formation by coating from a stable
somewhat modified to obtain PANI [108] and PPy [109] CP powders PEDOT dispersions and is currently limited only for PEDOT:PSS dis
can sometimes be used to obtain CPHs where a CP powder is added into persions because of its higher stability [124]. Interpenetrating polymer
a reaction mixture giving the final hydrogel product and has been used networks (IPN) of PEDOT-PSS hydrogels that are mostly fabricated by
to obtain CPHs based on CPs like PANI [110] PPy [111] and PEDOT mixing or in-situ polymerization using a non-conductive hydrogel
[112]. platform [125–128]. Due to significant delimiting effect of
non-conducting hydrogel network that at times functions like an insu
1.3.3. Method 3 lator (deionized water with conductivity value below 1 S cm− 1) and as
In this method (Fig. 2(c)) the CP monomers and hydrogel precursors such the electric conductivity is somewhat compromised [126–129].
are placed in the same vessel and simultaneous polymerization is carried The use of conductive nano-fillers, such as metal nanoparticles/wires,
out. This route involves the simultaneous polymerization of non- carbon nanotubes, and graphene have been employed to enhance the
conductive hydrogel and conductive polymer precursor or polymeriza conductivity however there is a limited use of such dispersed nano-fillers
tion via a two step mechanism by chemical or electrochemical oxidation. due to issues such as loss in uniformity of mechanical and electrical
This method was previously employed for the synthesis of PPy–pHEMA properties, and cytotoxicity to bio-systems [130–139]. Interestingly the
hydrogels. The addition of monomers such as acrylate, methacrylate and reports of PEDOT in combination with PSS has appeared as a strong
acrylamide monomers offers a better way to modulate the properties of candidate for emerging applications and has been successfully investi
these conducting hydrogels [113]. The representative examples gated offering numerous advantages apart from giving stability to
involving this route are PAAm polymer with BAYTRON-PR (PEDOT:PSS) aqueous PEDOT solutions while maintaining most of its properties. The
as conducting polymer and other example is chitosan polymer with inter-polymer complex formed between PEDOT and PSS produces a
PANI as conducting polymer [114]. The methods discussed above have solution/dispersion in water with good stability and hence the polymer
their own advantages and disadvantages; however the choice of the can be cast into desirable structures like films/coatings [130,131]. This
successful method for a network formation is significantly reliable on system retains excellent redox pattern, electrical conductivity
the final application output. Using these methods, the production of (1–10 S cm-1) and other important properties like that of PEDOT
conductive hydrogel can be achieved through in-situ polymerization [132–134] maintaining its application domain for wide number appli
technique of CP’s into pre-formed three-dimensional hydrogel network. cations like electronic devices. A product commonly known as ’Bay
The conventional methods for fabrication of CPH’s involve both con tron®’ is a patterned form of PEDOT:PSS given by Bayer AG. PEDOT:PSS
ducting polymer and non-conducting hydrogel component that some re-dispersible formulations have been recently launched by Agfa Mate
times leads to loss of electrical properties with the passage of time. rials who are working with conducting polymer materials commonly
Further the uses of metal in high quantities for polymerization some known by name Orgacon™ [135]. These dispersions of PEDOT:PSS with
times diminishes the compatibility of these systems. Thus the methods good stability has been applied in numerous fields with good commer
given above may have potential limitations that may reduce their use. A cial applicability. These PEDOT:PSS dispersions have high commercial
new method of hydrogels synthesis has recently been reported by Bao market worldwide with high utility in fields like optoelectronic devices
and coworkers [115] with maximum number of advantages such as high such as photovoltaic cells, LEDs and electrochromic displays [136–139],
processability, high values of conductivity and biocompatibility. The and has been used in inkjet printers as ink [140] and so on. Fig. 3(a)
authors have used phytic acid as a gelator that forms a strong polymeric shows structures of PEDOT in undoped and doped forms. New electronic
network without the use of non-conducting polymers. The phytic acid states (polarons and bipolarons) are presented in the band structure of
inherently possesses high ability to interact with conducting polymer this polymer as a result of doping giving rise to numerous transitions like
chains hence leading to strong gelation with gap for easy tunning of the new optical transition with broad band is observed in infrared region.
reacting components. The conductivity values obtained for PANI with Similarly Fig. 3(b) shows structure of PEDOT:tos and Fig. 3(c) shows the
Phytic acid were as high as 0.11 S cm-1. The hydrogels where able to be structure of PEDOT:PSS [141].
designed into micropatterns with excellent processability with applica
tions in glucose sensing as well. 2.1. Importance of functionalization of CP’s
2. Role of PEDOT and PEDOT:PSS in CPH’s Recently there have been reports of various strategies to achieve
PEDOT functionalization that is attractive strategy to form new kind of
Poly (3, 4-ethylenedioxythiophene) is a conducting polymer with hydrogels. Functionalization of dioxythiophene monomer has been
4
Fig. 3. (a) Schematic for undoped PEDOT and the corresponding band structure evolution (right): electron transfer (e-) to the undoped polymer (top) leads to the
formation of a polaron (middle) and finally a bipolaron state counterions “C” ensure charge neutrality. (b) Chemical structure of PEDOT:tos and (c) PEDOT:PSS either
chain carries one bipolaron.
Reprinted with permission from (Chem. Soc. Rev., 2016, 45, 6147–6164) copyright (2016) Royal society of Chemistry.
reported [142,143]. There are other attractive strategies proposed and These systems could give an advantage in controlling and tuning the
used by Zhu and coworkers using EDOT-OH for preparing functionalized properties of hydrogels required for a desirable application. The PEDOT
PEDOT copolymers, formed by EDOT-PC (phosphorylcholine) and functionalization with PDLLA shows desirable surface properties and
EDOT-MI (with maleimide), with capacity to mimic biological mem charge as such are potentially promising candidates for scaffold mate
branes and shows a high recognition rates of binding to target cells rials particularly for neural tissue engineering areas of interest [148].
[144]. Similarly acid functionalized PEDOT (refer to bio-electronic applica
It is reported that polyester biodegradable polymers are featured tions part of PEDOT CPH’s [79] that gives us an advantage over PEDOT
polymers for desirable application expected to be due to their biocom for fabrication of electro-conductive hydrogels with characteristic
patible nature. Among their large group the best studied [99,144] are swelling disposition, good mechanical attributes, active at physiological
polyglycolide, polylactides [poly (L-lactic acid) (PLLA), poly (D-lactic conditions and appropriate for propagation and differentiation of cells
acid) (PDLA) or poly (D, L-lactic acid) (PDLLA)] and polycaprolactones. (like: C2C12). T here are several reports of preparation of pure forms of
Highly crystalline nature of PLLA prevents it from degradation than its PEDOT-PSS hydrogels in view of various challenges hence avoiding the
counterpart PDLLA. What is more, the size and thickness could directly use of non-conducting hydrogel template [149], however a challenging
affect the hydrolysis reaction of PDLLA. Schmidt and co-workers [144] factor still harbors these systems like low electrical conductivity
proposed following degradable polymer (poly (< 10 S cm− 1), poor stability under wet physiological conditions due to
pyrrole–thiophene–polypyrrole). Jing and coworkers [99,144] have lack of supporting matrix. We will try to mention recent reports on the
provided a platform for approaching towards the copolymer synthesis, modulation in electric and mechanical properties of such systems by
as such a huge number of such modified copolymers have been devel simply employing different solvents and different application prospects
oped, via mixing of pentamer of aniline conducting polymer and with a of these hydrogels.
PLA triblock, briefly depicted as PLA-b-AP-b-PLA.PEDOT being one of
the other alternative polymers useful in biomedical applications and has 3. Applications of PEDOT and PEDOT:PSS CPH’s
displayed the constant conducting behavior in whole pH range [144].
Scaffolds with better biocompatibility for tissue engineering appli 3.1. Energy storage and supercapacitor applications
cations are challenging to design. PEDOT itself is a good alternative for
most of biomedical applications, as being electroactive in the whole pH 3.1.1. PEDOT based CPH’s
range while as PANI-based polymers possess some amount of cell Chen and coworkers [71] used concept of flexible supercapacitors
toxicity as their conductive emeraldine forms are stable only around pH involving PEDOT with other materials displaying attractive features.
4, hence restricting their role in various biomedical applications Because the flexible solid state capacitors work efficiently with high
[145–147]. Taking the advantage of importance of surface chemistry power density, greater stability and quick charge-discharge character
and charge da Silva and coworkers reported a strategy to synthesize a istics. Keeping in view the various limitations of CPH’s including lower
novel electrically conductive, biodegradable and biocompatible operating voltages with low energy density and use of potentially toxic
PEDOT-co-Poly (D, L-Lactic acid) (PDLLA) copolymer bearing dual acidic, alkaline or ionic liquid electrolytes. Here authors have investi
properties of two homopolymers in one system. PEDOT copolymeriza gated fully the fabrication of flexible supercapacitors using PEDOT and
tion was carried with number of materials with desirable properties with PVA via a self-assembly process utilizing dynamic nature of boronate
very low cytotoxicity for embryonic cells (E14.tg2a) that was assessed ester bonds shown in (Fig. 4(a)) Since of PVA-Na2SO4 [149] part from
by exploring the adhesion, migration and cell propagation regimes. having ecofriendly nature also displays the higher operation voltage
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window acting as safe electrolytes for fabrication of supercapacitors. and electrical properties of CPH’s. This type of system overcomes the
Therefore authors have designed a PEDOT-PVA hydrogels that main limitation of low electro-activity and mechanical performance of
tains strong electro-activity with neutral solid state electrolyte. A solid hydrogels. The presence of acid promotes the conformational changes in
state capacitor was so designed operating under voltages ranges of upto PEDOT with the result the 3D network of PEDOT sheets with PANI
1.4 V and offering high energy density of upto 15.2 Wh kg− 1 (based on chains comes out with enhanced mechanical properties due to strong
the total weight of PEDOT in the device). The promising nature of this interactions between PEDOT and PANI. The flexible supercapacitor
capacitor was demonstrated by its capacitance maintenance around fabricated from PEDOT/PANI system shows high energy density
89% and ~ 100% after 1000 charge–discharge cycles and mechanical approximately 0.25 mW h cm-3 at a power density of 107.14 mW cm-3.
folding cycles with scan rates of 5 A g− 1 with display of 100% coulombic This shows an improved version over other systems based on PEDOT and
efficiency. other systems including several other conducting polymer and GO as
Structural characterization carried out by FTIR and Raman spectra well.
showed PEDOT in a doped state with quinonoid structure confirmed by A very rich chemistry of PEDOT microparticle system has been uti
peak at 1357 cm− 1. B‒O‒C bond peaks at ~ 1220 cm− 1 gives evidence lized in preparation of stretchable and low density electrodes in a
of boronate ester structure in the hydrogel. From the Raman spectrum of multistep process. Armelin et al. have reviewed the exploitation of
PEDOT–PVA hydrogel. The peak at 1432 cm− 1 (symmetric stretch properties of biohydrogels for supercapacitors [150]. Biohydrogel sys
Cα = Cβ), shows strong conjugation in PEDOT chains and it can be tems are greener as well as cost effective. Following the same principle
inferred that PVA has least effect on structural form of PEDOT chains M.C.G. Saborio et al. [73] synthesized and investigated the super
with the result the electrical conductivity of the hydrogels is maximized. capacitor property of OESC devices carried out through combination of
In contrast, as discussed the commercial form of PEDOT–PSS displays PEDOT electrodes and different biohydrogels (i.e. sodium alginate,
strong peak at ~ 1441 cm− 1 indicating a significantly conjugation κ-carrageenan, gelatin, and chitosan. The two step procedure involves
length of PEDOT in the hydrogel. The softness and rubbery texture in loading of PEDOT microparticles into poly-γ-glutamic acid (γ-PGA)
hydrogels is due to presence of PVA with porous like coral morphology. hydrogel matrix in presence of biolinker cystamine. After this step a
The diameter of pores in the hydrogels ranges 50–100 nm (Fig. 4(b) left) chronoamperometric synthesis of poly (hydroxymethyl-3,4-ethyl
thus helping to achieve easy mass transfer and exchange of ions within enedioxythiophene) (PMEDOT) is achieved with help of PEDOT
the PEDOT–PVA hydrogel. The conductivity value was reported to be dispersed particles inside the hydrogel. The capacitance performance
nearly 0.9 S cm− 1 showing the importance of an interconnected network was revealed to be dependent on the conditions like time taken in
morphology and porous structure on conductivity and better electro polymerization reaction for synthesis of PMEDOT. Given a polymeri
chemical display of PEDOT–PVA hydrogel. zation time of 7 h supercapacitor performance of 45.4 ± 0.7 mF cm-2
Nevertheless, the reports of low electrochemical performance or was achieved by measurements through cyclic voltammetry and charge
mechanical properties of hydrogels poses a limitation in fabrication of discharge experiments. This electrode system coating with affordable
flexible solid state supercapacitors. Sometimes the mechanical proper bio-hydrogels has good potential in harboring challenges in designing
ties are compromised for conducting hydrogels and as such the suit light weight, stretchable electrodes hence giving us a new system for
ability for designing SSC is somewhat compromised. Taking the disposable electronic devices.
cognizance of these limitations Chen and coworkers [75] reported a
useful method invoking the effect of amalgamation of two kinds of 3.1.2. PEDOT:PSS based CPH’s
conducting polymers linked via a phytic acid bridge on the mechanical Different strategies of developing conducting hydrogels for energy
Fig. 4. PEDOT–PVA hydrogel. (a) Synthesis of PEDOT containing boronic acid moieties. (b) PEDOT–PVA hydrogel at three length-scales: (left) a photograph of the
hydrogel, (middle) a SEM image of the hydrogel showing the porous structure, and (right) a diagram showing the cross-link between PEDOT and PVA through
boronate bonds.
Reprinted with permission from (ACS Applied Energy Materials. 1(8) (2018) 4261–8 copyright (2018) American chemical society.
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storage purposes possess number of disadvantages like lack of conduc authors used the air dried fibers of PEDOT: PSS after treatment with acid
tivity and less number of desired structures rendering less viable for such as electrodes for fabrication of current-collector- free fiber based solid
applications. Thus authors have addressed this issue by using a strategy state capacitor (SSC) [151,152]. The fiber is strongly conducting and
of treating conducting hydrogels with acid in order to enhance the porous in nature with high mechanical strength. The fabricated super
conductivity values. Here Shi and coworkers [69] have developed a capacitor based on fiber electrodes show high capacitance performance.
supercapacitor using PEDOT: PSS conducting polymer. The modulation The performance parameters of this capacitor are much higher with
in conductivity has been carried by using H2SO4 as solvent and the group values of 202 F cm− 3 at 0.54 A cm− 3. The changes in the mechanical
have shown the influence of simply changing of the solvent on the properties of acid treated hydrogels may be thought due to acid induced
conductivity of PEDOT: PSS system. The reported conductivity values of conformational changes in PEDOT structure to expanded coil structure
PEDOT: PSS at very low solid content (0.78%) are as high as 46 S m− 1 with much stronger physical crosslinks and the heat treatment enhanced
and conductivity was so strongly enhanced upto 880 S m-1 (at 4% solid the gelation process. EDOT coil chains in a random form or doped state
Content) when treated with H2SO4. The preparation pathway involves each with magnetic spin of (1/2), while expanded coil represent or favor
treatment of PEDOT: PSS with sulfuric acid (0.1 mol L-1) while heating spinless bipolarons structure [153]. The calculated values of tensile
the mixture to 90 ◦ C.The reaction progresses with partial removal of PSS strength, Young’s modulus and toughness as high as 280 MPa, 6.5 GPa,
with sulfuric acid. An important property of these hydrogels is their and 26.17 MJ m− 3. Further the microporous morphology helps in im
flexibility and can be molded into different forms and shapes such as mediate formation of double layers. Fig. 5 shows the images of prepared
films, fibers, and columns with any size for different applications. The hydrogels casted into different geometrical patterns and also SEM im
presence of 0.78 wt%, solid content in PEDOT: PSS system signifies the ages of corresponding hydrogels before and after acid treatment. The
polymer has lower critical concentration of gelation (CCG) lower than two similar fibers were coated with PVA/H2SO4 gel electrolyte for
other conventional polymers such as poly (vinyl alcohol) (PVA) with construction of SSC as electrodes by twisting of each fibers over each
12 wt% solid content. The π-stacking interactions between PEDOT other characterized by cyclic voltammograms (CVs) with
chains may be the cause of lower CCG value with conductivity values quasi-rectangular shapes for the SSC even at a high scan rate of 1 V s− 1
greater than most of the reported CPHs (11 S m− 1). The untreated (Fig. 6(a)–(d)). The rate performance of current-collector-free fiber
hydrogel possesses a 3D network structure with wall (dense PEDOT:PSS supercapacitors displayed lower quality performance [154–157] and
nanosheets) thickness and pore diameter of 180 nm and 80 µm (Fig. 5 may be caused due to lower conductivity values of electrodes and
(f)). Volume shrinkage was observed upto 75% due to reduced pore size inefficient ion transport within the device. The triangular shapes of
(40 µm) and increased wall thickness around 470 nm (Fig. 5(g)). The galvanostatic Charge–discharge curves signify a fast and reversible
viscosity and modulus of AT-hydrogel showed about tenfold increments electron/ion movement with 95–100% coulombic efficiency. The gal
(Fig. 5(h)). After treating the hydrogels with concentrated H2SO4 vanostatic charge–discharge curves of the solid fiber supercapacitor
(18.4 mol L− 1) the conductivity values increases to 880 S m− 1 followed have a typical triangular shape with a high Coulombic efficiency of
by contraction in volume about 75% resulting in reduced average pore 95–100% (Fig. 6(e)), indicating a rapid and reversible electron/ion
dimension to 40 µm. The acid treated hydrogels have strong potential in transport. The performance of supercapacitor is calculated in terms of
different fields like electro-catalysis, energy storage, sensors, and actu volumetric or areal capacitance (CV or CA) (Fig. 6(f)). The capacitance
ators due to their unique properties such as very high conductivity and performance is much higher with 67% in retention of capacitance and is
3D porous morphology. Exploiting the properties of this system the very high than all the reported current collectors fiber supercapacitors
authors have used the same system for supercapacitor applications. The (1–50 F cm-3) reported previously. Finally it can be concluded that the
Fig. 5. (a–e) Digital pictures of PEDOT: PSS hydrogels with different geometric shapes (f and g) Cross-section SEM images of a freeze dried PEDOT:PSS hydrogel
before (f) and after (g) the treatment with concentrated H2SO4.
Reprinted with permission from (Advanced Materials (2017), 1700974) copyright (2017) Wiley online Library.
7
Fig. 6. (a and b) SEM images of dry fiber acid treated hydrogels. (c) Schematic diagram and (d) Intertwisted SEM image of a SSC. (e) Galvanostatic charge–discharge
curves of this fiber supercapacitor (f) Comparison of the volumetric capacitance of PEDOT:PSS fiber supercapacitor with those of previously reported counterparts,
SWNT = single-wall carbon nanotube, CNT = carbon nanotube, N-rGO = nitrogen doped reduced graphene oxide; CMC = sodium carboxymethyl cellulose and
CF = carbon fiber. g) Testing of fiber supercapacitor by repeated number charge/discharge for at least 10,000 cycles.
Reprinted with permission from (Advanced Materials 2017, 1700974) copyright (2017) Wiley online Library.
superior performance of this supercapacitor device cannot be neglected scan rate of 50 mV s− 1. The recycling efficiency was found out to be
reasonable due to high volumetric capacitance and high rate perfor approximately with 84.9% capacitance retention after 2000 cycles.
mance typical examples are compared in (Fig. 6(f)).The SSC is electro Excess PSS moieties provide strong electrostatic interactions with the
chemically stable with least change in capacitance performance after 10, metals cations due to presence of negatively charged groups in PSS like
000 cycles of galvanostatic charge discharge at 11 A cm-3 shown in SO−3 or SO3H groups (Fig. 7(a)), hence provide a facility for rapid
(Fig. 6(g)). The conductivity of acid treated hydrogel showed increasing gelation process of PEDOT:PSS like authors have used Mg2+ ions pre
trend for CPH’s being higher than reported carbon based hydrogels viously reported [163]. Since Mg2+ ions can only bind at most two PSS
[158,159]. The structural modulation upon acid treatment is primarily chains hence results in weaker gel network of PEDOT:PSS. The excess
related to the conformational changes of PEDOT from random coil Al3+ used by the authors shows excellent binding capacity (Fig. 7(a))
(benzene structure) to that of an expanded coil structure (quinonoid) linking simultaneously with three polymer chains resulting in strong
leading to stronger interchain interactions in a physically bound 3D PEDOT:PSS hydrogel skeleton. SEM images (Fig. 7(b)) show freeze-dried
network. The Raman spectrum reveals shifts in band at 1429 cm− 1 (due PEDOT: PSS hydrogels with a 3D porous network structure of pore size
to Cα = Cβ stretching vibration of thiophene rings) to 1424 cm− 1 [160, ~ 50 µm. The electrochemical properties were subsequently explored
161]. Based on different observations carried through different tech after modulation with secondary dopings with ethylene glycol (EG) and
niques such as electron spin resonance, X-ray photoelectron spectrum m-cresol vapors. The hydrogels, dark blue color with 94.4%, could
(XPS), Raman Spectroscopy, UV and FTIR it was finally confirmed that retain their shape with no visible volume changes as shown in (Fig. 7
the acid induced conformational changes in PEDOT: PSS complex (c)). Fig. 7(d) shows CV curve of PEDOT:PSS after treatment with EG and
removing PSS partially from the system. The increased solid content and m-cresol displaying enhanced capacitance performance (~ 3.3 times
further removal of PSS (soft content) enhanced mechanical strength of higher than EG treated hydrogels) in case of m-cresol doping which is
the hydrogels. This would enhance the π–π stacking and hydrophobic obvious from a rectangular-shaped CV curve. The overall electro
attractions between PEDOT chains that could also be influenced by chemical properties of the PEDOT:PSS hydrogel film enhanced by
increasing temperature leading to hydrogel formation in short period of organic solvent treatment is a result of secondary doping’s [164]. The
time. effect of m-cresol doping is more substantial due to its high polarity and
The effect of metal ions crosslinking in conducting hydrogels may such effects may be ascribed to the much better orientation of the
give an advantage over other systems. As such Song and coworkers PEDOT chains due to conformational transition from random coil
[162] have reported a new way of crosslinking conducting polymers of structure to an extended coil structure. Thus the hydrogel film obtained
PEDOT:PSS using metal ions. The gelation was quickly carried out by after secondary treatment with m-cresol results in much higher elec
using high concentration of Al3+ (2 M) to form a 3D network hydrogel trochemical performance important for supercapacitor applications
with approximate water content of 94.4 wt%. The multiple treatments with capacitance retention of 84.9% of initial capacitance at the end of
after the gelation showed good effect on conductivity of PEDOT: PSS 2000 cycles showing high cycling stability.
hydrogel film. As it was investigated that a highly conductive hydrogel The interest in fabrication of self-healing hydrogels has thickened the
film was achieved after soaking in ethylene glycol for some period of dimensions of hydrogel technology because of their inherent capacity of
time. Similarly authors carried out a first time study of such systems in prolonging service life and avoiding fatal failure. Although the chal
m-cresol revealing the enhanced capacitance values about 158 F g− 1 at a lenges of balancing the self-healing efficiency and mechanical properties
8
Fig. 7. (a) Chemical structure of PEDOT: PSS hydrogel formed by Al3+-induced cross linking. Optical photograph of PEDOT: PSS (b) the as-prepared PEDOT: PSS
hydrogel after 3 h. (c) SEM image of PEDOT: PSS hydrogel (cross-sectional view). (d) CV curves and (e) GCD curves of PEDOT: PSS hydrogel film electrode after EG
soaking treatment and m-cresol vapor treatment at a scan rate of 100 mV s− 1 in 0.5 M H2SO4 solution (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article).
Reprinted with permission from (Materials Today Communications 24 (2020) 101090) copyright (2020) Elsevier.
in hydrogels is still not understood fully. It is pertinent to mention here hydrogel due to higher number of physical linkages like hydrogen
that Liu and coworkers [72] present a report on highly stretchable, bonding as presented in (Fig. 8(B)) (X = 0(0 μL), 3(15 μL), 5(25 μL)
self-healing and mechanically strong hydrogels as a results of multiple from left to right in turn) and (Fig. 8(C)). The hydrogel is rendered dark
number of crosslinks by glycinamide side chains by monomer of in color after doping process showing strong binding of PEDOT: PSS
N-acryloyl glycinamide (NAGA). The polymerized NAGA hydrogels or within the network (Fig. 8(C)). Further SEM images reveal uniform
PNAGA hydrogels also demonstrated the huge recovery of mechanical distribution of PEDOT:PSS particles in the matrix. The high mechanical
strength due the hydrogen bonds tunable under heating and cooling strength could be revealed by its non-swellable nature in PBS with
conditions. Further the self –healing properties in hydrogels allow easy mechanical stability (0.22–0.58) MPa tensile strength (1.02–7.62) MPa
and tunable maneuver over multiple shape and pattern formation. The compressive strength, and (817–1709)% breaking strain. The doping in
hydrogel is formed by doping poly (N-acryloyl PEDOT/PSS leads to significant improvement in number of properties
glycinamide-co-2-acrylamide-2-methylpropanesulfonic) (PNAGA- such as increased specific conductivities but also displayed reversible
PAMPS) into PEDOT:PSS systems. The hydrogels possess dual amide sol-gel transition and self-healing character. Such supramolecular
cross-linking modes that leads to stronger supramolecular hydrogel. hydrogels possess high recovery and can be changed to any shape using
Here the poly (N-acryloyl glycinamide) PNAGA polymer serves both as 3D printing technique. What is more, the research group have also
the backbone for conducting hydrogels as well as crosslinker of co fabricated printable electrode using activated charcoal blend with the
polymers. A copolymerization process was carried between 2-acrylami PEDOT:PSS hydrogels under melting conditions. The capacitor perfor
de-2-methylpropanesulfonic acid (AMPS) and N-acryloyl glycinamide mance formed via conducting hydrogel electrodes possess high capacity
(NAGA) to form poly(NAGA-co-AMPS) PNAGA-PAMPS (Fig. 8) with and as such these hydrogels with high cytocompatibility possess a high
modulation in properties such as swelling and conductivity. However potential in applications like electro-active and electrical biomaterials
the thermoplasticity due to hydrophilic nature of AMPS could pave a [72].
way for obtaining 3D printed hydrogel supercapacitors. The molecular
structures of NAGA, AMPS and PNAGA-PAMPS are presented in (Fig. 8 3.2. 3D printing and patterning applications of PEDOT CPH’s
(A)). The Raman and ATR-FTIR plots suggest doping of PEDOT/PSS in
the hydrogel matrices without leaking of the dispersion even when kept 3.2.1. PEDOT based CPH’s
in water for long time. Optimized hydrogels with 20 wt% aqueous so You and coworkers demonstrated a way for patterning of PEDOT in
lutions of PAMPS-PNAGA and PNAGA-PAMPS/PEDOT:PSS-X-49 solution phase including different substrates like indium tin oxide (ITO)-
(X = μL of PEDOT:PSS) were found to form stable supramolecular coated glass/film and hydrogels [165]. Authors described a three step
9
Fig. 8. (A) Schematic illustration of the molecular structures of N-acryloyl glycinamide (NAGA), 2-acrylamide- 2-methylpropanesulfonic acid (AMPS), and poly
(NAGA-co-AMPS) (PNAGA-PAMPS). (B) Gelation of aqueous solutions of PNAGA-PAMPS/PEDOT/PSS-X-49 (X = 0, 3, 5 from left to right in turn). (C) Schematic
description of the network structures crosslinked by dual amide hydrogen bonds and doped with PEDOT/PSS (For interpretation of the references to color in this
figure legend, the reader is referred to the web version of this article).
Reprinted with permission from (Scientific reports. 2017 Jan 30; 7(1):1–1) copyright (2017) adapted from nature publications.
strategy for facile synthesis of PEDOT hydrogels. Step one revolved hydrogel shows a promising nature for bioelectronics in detecting
around solution phase monomer casting and oxidative polymerization cellular functions. Fig. 9 describes a schematic description of prepared
being reliable in creating uniform PEDOT with high conductivity. Step CP patterns on either ITO glass or hydrogel substrate.
two involves constructing the PEDOT design by poly (ethylene glycol) After a gap of two more years a similar system was prepared by
(PEG) photolithography as PEG helps in contraction via photolithog simple modification of PEDOT based Pt electrode using electrodeposi
raphy by controlling shape and dimension of pattern. In nutshell this tion method. Hydrogels are securely fixed onto PEDOT-Pt substrates and
strategy proved highly promising in nature with advantage over other at same time a second PEDOT (low conductivity) layer was electro
patterned PEDOT systems like ecofriendly nature of process, econom deposited to hold the initially deposited PEDOT film to the hydrogel.
ical, and control over the process. What is more, an electrochromic (EC) Finally PEDOT micropatterns on hydrogels were successfully removed
device and flexible microelectrodes were also designed using CP pat using the electro actuation property of PEDOT. This system has a good
terns on hydrogels. This PEDOT based microelectrode containing property disposition with advantage of using mostly natural and
10
Fig. 9. Solution phase only process of fabrication of Conducting hydrogel micropatterns; (A)represents scheme of fabrication of CP patterns on ITO or hydrogel
substrate: (i) Casting and polymerization of EDOT (ii) PEDT photolithography (iii) Peeling PEG hydrogel (iv) CP pattern on indium tin oxide (ITO)-coated glass (v, vi)
Second gel precursor solution (agarose or PEG) was poured onto the PEDOT-patterned ITO glass and a second gelation was conducted (vi) Peeling of second layer and
transfer PEDOT pattern to PEG substrate (vii) CP on flexible hydrogel layer. (B) Photographs of (a) PEDOT films (b) Peeling off of the PEG hydrogel layer, (c) PEDOT
pattern on ITO glass, (d) Peeling off agarose gel layer, and (e) From of CP from glass to agarose hydrogel substrate.
Reprinted (adapted) with permission from (ACS applied materials and interfaces 8 (2016) 33175–33182) Copyright (2016) American chemical society.
synthetic hydrogels including agarose, collagen and polyacrylamide. phosphate buffered saline, as low Young’s modulus of ~ 2 MPa and high
The technicality and fabrication of dense PEDOT modified Pt films in stretchability of over 35% strain in wet physiological environments
volves an intelligent approach. For example, the use of CH3CN solvent achieved at (13 vol%) DMSO and annealing condition (three cycles of
directly leads to successful formation of conductive PEDOT, from EDOT 30 min annealing at 130 ◦ C) were displayed.These results showed long
with advantage of PEDOT bio-functionalization such as enzyme immo terms effects and a demonstration of a highly conducting, and stable
bilization. The electrochemical actuation property of PEDOT ( ± 0.5 V pure PEDOT-PSS hydrogels both in free-standing and tough coated
vs. Ag/ AgCl) system helps to peel off the PEDOT micropatterns from shapes with intricate patterns were easily enabled by this applaudable
platinum electrode [76]. method. The high patterning efficiency of this hydrogel is also high
lighted in Fig. 10 where (a) showing patterning of PEDOT:PSS on PET
3.2.2. PEDOT:PSS based CPH’s substrate and anisotropic drying process of the patterned ink over time.
In light of the numerous challenges like low conductivity, lower (b) Peeling the dry annealed pattern followed by swelling in PBS. (c)
stretchability and lack of supporting matrix with lower stability under Robust pattern achieved by suppressing delamination through aniso
wet physiological conditions due to lack of supporting matrix. PEDOT: tropic swelling behavior.
PSS hydrogels were fabricated using H2SO4 with conductivity values Bao and coworkers [166] presented a very beautiful way of
around (8.8 S cm-1) however the use of sulfuric acid for fabrication of patterning PEDOT:PSS conducting hydrogels using electrochemical
hydrogel followed by electrical conductivity testing under acidic con gelation known as (“electro-gelation”) with such a versatile way of doing
ditions (pH 1) renders it less suitable for bioelectronics application. In it on a any given template that includes large number of shapes such as
view of these limitations Zhao and coworkers at MIT [70] produced a curved and multidimensional surfaces. It was shown that by using the
hydrogel from PEDOT: PSS with surprisingly good electrical conduc sacrificial metal layer high resolution hydrogel pattern could be ach
tivity values, good mechanical and swelling properties by incorporation ieved. As such these high performance hydrogels could be easily intro
of the volatile DMSO followed by other important steps like dry duced into complex device frameworks [166]. PEDOT:PSS have an
annealing and rehydration. Thus helps in tuning the properties of these important characteristic of forming hydrogel in presence of sufficient
interconnected hydrogels. This was achieved by mixing of DMSO with availability of metal cations and thus favor electro-gelation phenome
aqueous PEDOT-PSS solutions. A system closely resembling the one with non. The tuning of ionic strength could control the gel formation due to
H2SO4 as solvent, however with totally different conductivity perfor aggregation via different interactions like π–π stacking interactions of
mance simply by presence of DMSO. The pure hydrogels were obtained PEDOT:PSS microgel particles. Based on this phenomenon the research
by employing a controlled procedure. The tunability of properties like group tried to employ this concept by using a sacrificial metal by elec
electrical, mechanical, and swelling was systematically done by con trochemically oxidizing the patterned metal layered to achieve control
trolling the added amounts DMSO and the way of dry-annealing. The over the ionic strength. Sacrificial metal is part of working electrode and
successful optimization in properties like the conductivity values could is oxidized to give cations, acting as gelators for PEDOT:PSS after
reach upto ~ 40 S cm− 1 in deionized waters, and ~ 20 S cm− 1 in passing into electrolyte. This work gives us the new concept of
11
Fig. 10. Patterning of pure PEDOT:PSS hydrogels (a) patterning of PEDOT:PSS on PET substrate and anisotropic drying process of the patterned ink over time. (b)
Peeling the dry annealed pattern followed by swelling in PBS. (c) Robust pattern achieved by suppressing delamination through anisotropic swelling behavior.
Reprinted (Adapted) with permission from (nature communications 10 (2019) 1043) Copyright (2019) Nature research Journal.
patterning the sacrificial layer into desired pattern on a given substrate poses a limitation to this technology. Here the authors make use of a
(conductive) (Fig. 11(a)) via metal evaporation method through shadow very common ionic liquid (IL) 1-ethyl- 3-methylimidazolium ethyl sul
masks. The patterned substrate was finally used as a working electrode fate (EMIM: ES) that simultaneously acts both as conductivity enhancer
for construction of electrochemical cell with PEDOT:PSS as aqueous and gelator. The hydrogels is formed by gelation of PEDOT: PSS/ IL and
electrolyte solution. Fig. 11(b) shows the graphite rod being used as patterning is achieved in-air coalescence of PEDOT: PSS and ionic liquid
counter electrode and Ag/AgCl as reference electrode. This is the basis of (IL). The conductivity values showed an intense buildup for printed
gelation of PEDOT:PSS as shown in (Fig. 11(c) and (d)). Hydrogels under films of PEDOT:PSS /EMIM:ES upto 711 S cm− 1 and the highest values
application of sufficient anodic potential leading to oxidation of sacri of 900 S cm− 1 conductivity was explored at 2.0 wt% of EMIM:ES. A
ficial electrode followed by increasing the concentration of metal ions highly controlled drops of PEDOT: PSS/IL are achieved with diameter as
leading to ionic strength variations hence favoring controlled ≈ 260 µm formed in a very short interval of time (≈ 600 μs) by strongly
patterning. The selection of copperas a sacrificial electrode could be controlling in-air location of drops and encapsulation by Marangoni
reasonable due to its less possible side reaction and formation of Cu2+ driven phenomenon. Thus the main advantage of MRIJP technique is
ions above 0 V and below stability window of water. Previously the that the in-air coalescence of PEDOT: PSS and IL causes formation of
group showed gelation induction in presence of Cu2+ to be faster than in hydrogels in a single moment hence removing Marangoni type of flow
presence of ionic liquid induced gelation [182]. However both of them behavior between reacting species on the substrate. Thus this technique
have their own advantages. The fast gelation in presence of electro demonstrates the huge capability of MRIJP for formation of composite
chemically generated Cu2+ ions offers high reliability in patterning the material while mixing in micrometer ranges with high precision.
PEDOT:PSS hydrogels (Fig. 11(e)). SEM technique was employed to Reasonably this technique has numerous advantages of freeform
confirm the hydrogels formation with porous structure. X-ray photo patterning and is somewhat identical in respect to those where fabri
electron spectroscopy (XPS) was used to confirm the removal of Cu2+ cation is carried out by spin-coating method. While using PEDOT:
ions from the hydrogel patterns shown by elimination of Cu 2p signal PSS/IL films as interchangeable electrodes of an alternating
intensity (Fig. 11(g)). current-electroluminescent (ACEL) device finally it is demonstrated the
The work carried by Stringer and coworkers [74] shows a way of use of MRIJP technique for preparing variety of 2D and 3D structures of
synchronizing printing and patterning of conducting films and hydrogels hydrogels with control over the design such as the one with a patterned
at same time into 2D and 3D structures on a nonporous substrate using electrode design and multilayer open channel structures processable in a
MRIJP (micro-reactive inkjet printing) technique. The tuning of gelation single step strategy solely demonstrated by this technique thus showing
in PEDOT: PSS has potentially broadened its application window in 3D advantage over other existing printing techniques.
printing and patterning applications, however the use of inkjet printing Since the ionic liquid used by the group (EMIM: ES) achieves a sig
poses a challenge while forming a gel because of high viscosity hence nificant result in modifying the viscosity and enhancing the gelation of
12
Fig. 11. PEDOT:PSS hydrogel patterning using electrogelation method.

Reprinted with permission from (Advanced Materials 31 (2019) 1902869) copyright (2017) Wiley online Library.
PEDOT: PSS solution. What is more the swelling studies in water for electrode applicable for cultivation of contractile myotubes. Authors
conductive hydrogels showed the increase in length from ≈ 10 mm to demonstrated successfully the application of this soft flexible electrode
≈ 20 mm after kept 30 min in water showing good swelling results. in C2C12 myotube stimulation. This work preparing PEDOT/agarose
Different 3D patterns could be achieved through MRIJP technique with electrodes is not limited to agarose system only but can be applicable to
pattern dimensions 0.2–0.5 mm (Fig. 12(a)). Tunnels and holes in other hydrogels as well such as collagen and fibrin [169]. Fig. 13 de
hydrogel patterned structures gives a glimpse of flexibility and capa scribes the hydrogel preparation and subsequent application for myo
bility of this technique (Fig. 9(b)). Authors achieved a Y-shaped and two tube stimulation. Fig. 13(a)–(c) gives schematic illustrations of the
parallel tunnel printed shapes where and at the same time a liquid can fabrication of a conducting polymer/hydrogel electrode: (a) Here a
easily flow as the hydrogel is flipped upside down (Fig. 12(c) and (d)). melted agarose solution is put on Pt microelectrode substrate (b) Fol
Based on the same approach adapted the printing of low viscosity ink lowed by PEDOT electro-polymerization (c) electrochemically actuated
can be designed into 3D structures. Thus the structural integrity of various times of peeling process. (d) Photographs show PEDOT micro
printed hydrogel is usually governed by mechanical properties weak in arrays on a gel sheet. Fig. 14(a) shows an experimental plan set up for
its nature and unavoidable to construct a more complicated structure. stimulation of myotubes. A fibrin gel sheet contains micro-patterned
The mechanical properties of hydrogels can also be controlled by using a C2C12 myotubes supported on the PEDOT/agarose electrode. Fig. 14
support or by using covalently crosslinked hydrogel [167,168]. Thus the (b) shows time progression of contractile displacements of C2C12
authors have made good analysis in 3D patterning and printing of myotubes (red) and the PEDOT hydrogel electrode (blue).
hydrogels applicable for bioelectronics and printable electronics. An innovative porous CH with live cell monitoring properties was
fabricated using PEDOT CP and Xanthan Gum with biocompatible na
ture as supporting polymer. There is good agreement that CP scaffolds
3.3. Bio-electronic and tissue engineering applications of PEDOT CPH’s stimulate and help in growth of cells like neurons, muscle cells and heart
cells. The cell growth within the scaffold can be monitored by mea
3.3.1. PEDOT based CPH’s surement of impedance which is successful tool for considering this
A PEDOT/Agarose based CH was prepared by simple micro activity. The authors framed this system utilizing PEDOT-xanthan gum
patterning of PEDOT on agarose hydrogel forming a fully flexible, moist
13
Fig. 12. (a) Solid tree, rectangle, and triangle (20 layers). (b) With 4 hollows and its microscopic image (10 layers). (c) Y-shaped open channel and its microscopic
image (10 layers). (d) Two parallel open channels and fluid flow during lifting (10 layers).
Reprinted (adapted) with permission from (ACS applied materials and interfaces 11 (2019) 37069–37076) Copyright (2016) American chemical society.
instead of the well-known PEDOT-polystyrene sulfonate scaffolds. A could offer a range of enhanced properties. The authors have given first
normal reaction was initially carried out in presence of stabilizing agent such report where a conductive network hydrogel was formed from
xanthan-gum called as oxidative polymerization of PEDOT. The porous covalently linked conjugated and hydrophilic polymers. The previous
structure was found to be tunable by controlling the amount and approaches show the drop in electroactivity of conducting hydrogels due
formulation of the starting PEDOT-polysaccharide dispersion. Scaffolds to leaching out of toxic CP’s [170]. Similarly ionic CP’s face the same
porous size ranges between 10 and 150 µm and low young’s modulus. challenges including leaching and are being neutralized at pH = 7.4
Authors successfully showed the working of scaffolds in supporting the thus causing loss of important properties [171]. The development of
three dimensions cultures cells (MDCK II eGFP and MDCK II Life Act non-hybrid conductive hydrogels can be achieved through various
epithelial cells) with good cell attachment results and high pore routes including self-assembly of polymeric chains, chemical cross
coverage. This could easily be monitored by simply measuring electric linking methods, and freeze drying of CO dispersions or using low mo
impedance of the synthesized PEDOT scaffolds [78]. lecular weight gelators (LGs). The hydrogels obtained as such usually
Stevens and coworkers [79] reported a new carboxylic functional have faster electron transport between the conjugated chains as there
ized PEDOT 3D electroactive hydrogels. Such a system could easily be are fewer insulting polymers in the matrix. However there are numerous
linked to various hydrophilic polymers with good swelling capacity and challenges harboring such procedures that limit its use in tissue engi
soft mechanical properties rendering it a promising material for 3D neering applications particularly considering the use of self-assembly
scaffold applications. The PEDOT was chemically functionalized with procedure in fabrication of hydrogels. Further the issue of stability in
hydrophilic functional groups having water soluble properties. The physiological conditions is still not fully investigated as ionic strength
resultant functionalized PEDOT conducting polymers offers easy post may somewhat effect the overall network structure and its assembly
functionalization tunable for successful and desired scaffold applica resulting in changes in physiochemical properties of the hydrogels.
tions. The copolymerization of functionalized EDOT with acrylic acid Hence the authors have given a new strategy to avoid loss of CP chains.
14
Fig. 13. (a) Here a melted agarose solution is put on Pt microelectrode substrate (b) Followed by PEDOT electro-polymerization (c) electrochemically actuated
various times of peeling process. (d) Photographs show PEDOT microarrays on a gel sheet.
Fig. 14. (a) Experimental setup for stimulation

of myotubes. A fibrin gel sheet containing the
micro-patterned C2C12 myotubes is laid on the
PEDOT/agarose electrode. (b) Time course of
contractile displacements of C2C12 myotubes
(red) and the PEDOT hydrogel electrode (blue)
(For interpretation of the references to color in
this figure legend, the reader is referred to the
web version of this article).
Reprinted adapted with permission from (JACS
9 (2010) 13175).Copyright (2010) American
Chemical Society.
PEDOT with pendant functional carboxylic groups (PEDOT-COOH) less useful for tissue scaffold applications. The authors selected PEDOT
meets nearly all the requirements with properties such as: solubility, due to its stability in aqueous solutions with good biocompatibility.
easy post-functionalization modification, retention of electronic prop Further the presence of carboxylic moieties allows enhanced overall
erties post gelation process as such a represents a system with good swelling for developed scaffold. Since functionalized PEDOT (f-PEDOT)
future prospects. Further limitation of electro-polymerization (used on is potentially a strong candidate for tissue engineering applications due
electrode surfaces only) has been addressed by using chemical poly to high swelling and mechanical strength. The redox activity of the
merization technique. The alkyl, alkoxy and alkyl-sulfonates derivatives f-PEDOT is important for production of electrical stimulus. The CV plots
of EDOT have limited their use to post-functionalization issues as such show characteristic features. A broader anodic and reduction peaks
15
show effective transport occurring in f-PEDOT even in swollen as well as cells was observed and is expression or marker for maturation of C2C12
in presence of insulating polymers (PAA and PEG). Following doping cells. Further investigation showed both doped and undoped states were
with 0.1 M HClO4 the CVs showed reversible behavior showing high favorable for maturation of these cells. In conclusion expression of MHC
rates of charge transfer occurring significantly due to higher conduc IIb protein (Fig. 15(c)) and Ki67 (Fig. 15(a) and (b)) indicated that these
tivity in a doped state. The results further showed that the doped and hydrogels were capable of supporting the differentiation of C2C12 cells.
undoped hydrogels were having firm contact with the electrode surface. Koh and coworkers [80] explored a PEDOT based hydrogels for
The electroactive properties of aqueous solution of f-PEDOT scaffold C2C12 myoblast stimulation. A novel PEG based hydrogel was able to be
were well retained hence represents good features for differentiation micro-patterned where hydrogel was prepared through micro-molding
and proliferation of C2C12 cells. The cell adhesion was easily achieved technique. The technique involves synthesis of PEGylated-PEDOT
in f-PEDOT hydrogels without using external coatings/precoatings. The hydrogels using PEG hydrogel microgroove structure with ridges and
morphological composition of C2C12 cells was witnessed by using grooves of 3 µm each and finally the PEDOT based hydrogels were
phalloidin stain used for actin showing no damage to structural network formed by in-situ polymerization of EDOT and micro-patterned PEG
of both doped and undoped cells (Fig. 15(a) and (b)). Ki67 protein is hydrogels. In nutshell a structurally well-defined micro-grooved
present during all cell cycles and can be exploited after staining for conductive hydrogel based on PEDOT is achieved having conductivity
investigating cell proliferation (active phase and absent in resting cell). values of 2.49 × 10–3 S cm-1 with 85% water content. The PEDOT-PEG
The cells allowed to grow in hydrogels were progressively observed and conducting hydrogels revealed greater resemblance to the muscle tis
were aligned at day 3 (Fig. 15(c)) with high multinucleated tubes at day sues having mechanical moduli values similar to them. The presence
7 (Fig. 15(c)). Further the production of proteins (MHC IIb) from C2C12 PEG in the conducting hydrogel imparts the cell adhesion properties
Fig. 15. Culture of C2C12 in f-PEDOT (a) proliferation of cells in undoped hydrogel (b) proliferation in doped hydrogels at day 3. Proliferation visible from positive
nuclear Ki67 staining (green), while phalloidin staining for actin (red) enables cell shape visuals. DAPI stain labels the DNA in nuclei (blue). C) Staining for the
mature muscle marker myosin heavy chain IIb (MHC IIb) (green) and DAPI (blue) in undoped and doped hydrogel at day 3 and day 7. Here C2C12s are somewhat
single celled at day 3, multicellular tubes day 7 showing growth of cells (For interpretation of the references to color in this figure legend, the reader is referred to the
web version of this article).
Reprinted adapted with permission from (Chemistry of Materials 28 (2016) 6080–6088). Copyright (2016) American Chemical Society.
16
without compromising the conductivity of hydrogel. The in vitro cell

assay revealed the good potential of hydrogels in tissue engineering
application. The investigation was carried on C2C12 myoblast cells and
the results showed growth of myoblast cells with better cytocompati
bility. The other conducting/no-conducting hydrogels of PEG without
microgrooves were found to have less effect on the myogenesis of C2C12
myoblasts. The positive effects were explored even in absence of elec
trical stimulation. However when the studies were carried out using
electrical stimulation the differentiation of C2C12 myoblasts was
enhanced showing the combined effect of structure and electrical im
pulses and hence revealing the essence of micro-grooved surface to
pology and importance of PEDOT conducting material in hydrogels.
Conducting and tough dual network hydrogels were reported by
employing PEG-methyl-ether methacrylate (PEGMA) and PAA. Elec
Fig. 16. Varying Physical and electronic properties of PEDOT in presensce of
tronically conducting polymer PEDOT was chemically bonded within
(i) Acrylic acid(AA) only (ii) Both Acrylic acid and Hydroxyethyl methacrylate
the hydrogel with maximum conductivity 4.3 S cm-1. The pH effect on (HEMA) (c) HEMA only.
different properties was studied. The tensile strength and compressive Reprinted (adapted) with permission from (ACS Appl. Mater. Interfaces 9(2017)
strengths were obtained as high as 0.6 MPa and 11.6 MPa. This pub 44124–44133). Copyright(2017) American Chemical Society.
lished article reports the highest conductivity for hydrogel with high
swelling ratios. Under cyclic compressions the electrical resistance 3.3.2. PEDOT:PSS based CPH’s
showed a significant change, hence they can potentially be utilized as Annabi and coworkers [77] prepared a conducting polymeric
soft strain sensor applications [172]. Before the said publication authors hydrogel using PEDOT:PSS solution dispersed in a photo-crosslinkable
reported conjugated conductive hydrogel/gel systems. Harboring vari hydrogels of GeIMA. The group has studied the influence of PEDOT:
able nature of electroactive species like PEDOT)-poly (Styrene-sulfo PSS concentration on physical and structural and cellular responses of
nate) (PSS), [173] PEDOT-PSS-polypyrrole (PPy), [174] PPy-PSS, hydrogels. The hydrogels were loaded with 0–0.3% (w/v) PEDOT:PSS
PEDOT-sulfonated polyaniline (SPANi), and PPy-SPANi [175,176]. concentration showing the tunning in the properties of hydrogels such as
Conductivity values were achieved as 10− 2 S cm− 1. The mechanical mechanical and swelling. The impedance behavior was particularly
spectra showed the dependence on composition. calculated showing decreasing trend from 449.0 kΩ for control GeIMA
Taking into consideration the importance of smart hydrogel based to 281.2 and 261.0 kΩ at 0.1% (w/v) and 0.3% (w/v) PEDOT:PSS at
sensing systems and keeping in view there promising application in 1 Hz frequency. The group has achieved good results for stimulating
sensing and health care systems. In view the challenges like lower strain contraction in explanted abdominal tissue connected with composite
sensitivity and lower anti-freeze properties Ma and coworkers [81] hydrogel. It was shown that compared to stimulation voltages of
proposed a novel organo-hydrogel sensor with higher gauge factor of up 9.3 ± 1.2 V for GeIMA the decrease in stimulation voltages could be
to 7 at strain rate of 100% and higher anti-freezing properties. The seen from 6.7 ± 1.5 V and 4.0 ± 1.0 V for hydrogels containing 0.1%
multifunctional electroconductive hydrogel was synthesized by using (w/v) and 0.3% (w/v) PEDOT:PSS concentrations. The hydrogels con
poly (acrylic acid) (PAA) skeleton with poly (3,4 ethyl taining 0.1% (w/v) PEDOT:PSS were tested for C2C12 myoblasts and it
enedioxythiophene): sulfonated lignin (PEDOT:SL) in dispersion me was revealed that the composite hydrogels could support the viability
dium containing binary mixture of water/glycerol. This work shows the and in vitro studies showed that composite hydrogels supported the
use of lignin with PEDOT following by integration of organo-hydrogel sustainability and distribution of C2C12 myoblasts, comparable to
for strain sensing. Moreover the organo-hydrogel being nontoxic with GeIMA controls. These results could help to design such materials for
results showing that the organo-hydrogel is able to prevent skin frost applications in electro-conductive biomaterials [77].
bites. Finally a soft hydrogel with conducting and self-wrinkled nature Fei-Peng Du and co-workers [178] working on the concept of SIPN
with better sensing is obtained. As prepared system not only senses the technology provided a stretchable and electroconductive system with
movement of limbs but also the weaker pulse and vibrational move high mechanical disposition eligible for bioelectronic applications such
ments of throat with good detection power for signals related with as wearable devices and other biological applications. The SIPN con
techniques such as electrocardiography (ECG) and electromyography ducting network system was achieved via chemical crosslinking of PVA
(EMG). with glutaraldehyde in presence of conducting mixture of PEDOT: PSS
Mawad and coworkers opened a new ways of forming functionalized medium. The investigation through FTIR, Raman, SEM and TGA
PEDOT using vinyl monomer based hydrogels. This PEDOT conducting revealed formation of SIPN conducting hydrogel system. The SIPN sys
polymer can be functionalized with vinyl monomers acrylic acid and tem displayed high tensile strength and compression properties. The
hydroxyethyl methacrylate that have different hydrophilic properties experimentally calculated values of tensile and compressive properties
used to modulate the electronic and mechanical properties of con SIPN of PVA with PEDOT: PSS were suggestive of strong SIPN hydrogels
ducting hydrogels. The electro-activity is found to be directly related to formed by the interaction of PEDOT:PSS and PVA. The tensile strength
composition of PEDOT hydrogel. The analysis of PEDOT structure and compression stress (50% Strain) values were (calculated at 0.14 wt
revealed an oxidized form that is very advantageous in giving its elec % PEDOT: PSS) 70 kPa and 216 kPa respectively. Further the swelling
trochemical behavior in physiological environments. This study gives a behavior and electrical conductivity was shown to be dependent on the
hint of application in the field of tissue engineering like tissue scaffolds concentration of PEDOT: PSS with reduced swelling properties at higher
for electroactive tissues. Fig. 16 shows the variation in oxidation po PEDOT: PSS hydrogels. The cumulative effect (high electrical conduc
tential and mechanical properties like variation of Young’s Modulus of tivity, mechanical properties and flexibility) of many properties of this
such hydrogels when AA (Acrylic acid) HEMA (Hydroxyethyl methac hydrogel sensor with gauge factor of up to 4.4 at percent strain of 100%
rylate) are used in copolymerization process. It is said that the presence making it promising material in fields of bioelectronics such as wearable
of hydrophilic monomer with more ionizable groups show increased sensors and flexible electronic skin.
repulsive interactions leading to more water inside hence weakening Xuetong Zhang and coworkers designed cryogels from pure PEDOT-
mechanical properties of the swollen hydrogel for example PEDOT-AA PSS systems. A three dimensional porous morphology and structure was
and PEDOT-AA-HEMA CH’s. However hydrophobic interaction lead to achieved by ice-segregation-induced self-assembly (ISISA) employing
increase in young’s modulus as was observed for PEDOT-HEMA [177].
17
different PEDOT-PSS freezing dispersion or a fabricated hydrogel. X-ray hydrogel. EES measurements reveal the easy elucidation of the func
photoelectron spectroscopy and Raman spectroscopy gave an insight tional effects of the PEDOT and in-vivo brain-derived neurotrophic
into the molecular structure. Novel disposition of properties was factor (BDNF) release studies were carried out to evaluate the efficiency
demonstrated through different techniques such as differential scanning of the hydrogel coating. Since BDNF has previously been studied with
calorimetry and conductivity measurements. Such macroporous system ample evidence for stimulating and promoting auditory nerve endur
shows a promising potential in designing and development of electronic ance following hair cell loss [192–197]. Finally it can be expressed that
parts catalytic activity and as a platform for separation process. These after a chronic implantation of this CPH coating showed good results due
conducting polymer cryogels with aligned/unaligned macroporous ar to long term stability, biocompatibility elucidated by EES and Cochlear
chitectures suggest the potential in the development of electronic histological analysis results.
components, tissue engineering, and next-generation catalytic and sep A transdermal drug delivery conducting hydrogel blend system
aration supports[179]. based on PEDOT/Alginate hydrogels reported by Paradee and co
Xu and coworkers [82] reported a PEDOT-PSS-Protein PEG based workers. The authors have investigated the effect of PEDOT morphology
system with capacity to achieve success in development of three on the transdermal release of benzoic acid from PEDOT-Alginate
dimensional cell cultures with electro-conductive nature. The systems hydrogels. All the properties of the CPH like cross-linker amount,
was approached by creating a sort of non-covalent interaction between PEDOT particle dimension and electric field strength were established in
Protein-PEG and conducting nanostructures enhancing its overall a modified Franz-diffusion cell to know the mechanism of benzoic acid
electro-conductivity, viscoelasticity and featuring molecular drug release and the diffusion coefficient. The effect of the crosslinking
self-healing phenomenon. This system could be characterized by dual that directly affected the mesh size caused some changes in diffusion
property disposition self-healing capacity and injectability. coefficient. Effect of electric field on diffusion coefficient highlighted the
elevated response due to simultaneous electro-chemical phenomenon.
3.4. Drug delivery applications of PEDOT CPH’s The best diffusion coefficients were achieved for the blend with low
dimension PEDOT particle and high electrical conductivity. The poten
3.4.1. PEDOT based CPH’s tial of such systems in transdermal drug delivery with high prospects can
Metal ions bound to CPH’s have been utilized for the release purpose be an option to be focused upon [85].
under variable physiological and electrical stimuli’s. Since Mn2+ given
as a subcutaneous injection in the concentration ranges (useful for MRI 3.4.2. PEDOT:PSS based CPH’s
analysis) proves to be highly cytotoxic with least control over the A must useful drug delivery systems that may offer a good suitability
amount diffused [180]. Regarding this challenge a CPH system based on for use in in-vivo applications must offer numerous advantages like high
PEDOT and chitosan was developed by Chen and coworkers [181] for drug loading capacity, with a large window for drug integration with
controlled release of Mn2+ ions. The electrically controlled release of variable size charge and solubility. Further a good focus on the me
Mn2+ has been used as neural interface for Manganese –enhanced MRI chanical and electrochemical stability of biocompatible coating will
for deep brain stimulation. The hydrogel could mimic the ECM with ensure their further processability like depositing them on electrodes
good physical and mechanical properties with electrochemical stability with variable efficient patterns [198,199]. CPH’s may be the suitable
and biocompatibility. Thus the tuning of the electrical intensity and candidate to answer these challenges [200,201]. The property of
pulse frequency can help an on demand trace release of Mn2+ for DBS swelling in water facilitates the accumulation of high concentration of
showing a distinct contrast on T1-weight image. biomolecules whereas CP ensures the electrochemical control of the
Conducting polymers like PANI and PEDOT have been used as in drug release. General drug delivery systems usually focus only some
terfaces between electrodes and tissues like neural tissues [182,183] and aspects of drug delivery parameters such as specificity single bio
provide electrical and ionic conductivity that directly depends on the molecules, less control over the drug release kinetics and difficulty
conjugated polymer backbone. Since conducting polymers can poten downscale fabrication process. Taking into consideration above limita
tially improve many properties of electrodes like impedances, reducing tion C.Kleber and coworkers [84] fabricate a drug delivery system, novel
scar tissue formation and help to enhance the overall charge transport in its kind addressing most of the limitations discussed above. This
[184,185] hence they can play a significant role in designing cochlear system is relatively different version over conventional PEDOT: PSS.
implants (CIs). The CP’s are intrinsically able to influence or control the These hydrogels were synthesized using copolymer of poly (dimethy
external environment closely surrounding the CI and hence can enhance lacrylamide-co-4-methacryloyloxy benzophenone (5%)-co-4-styr
electrical hearing [186]. Further hydrogels have been previously used enesulfonate (2.5%)) (PDMAAp) and the conducting polymer PEDOT.
across different domains in tissue engineering and regeneration and This copolymer materials shows very promising properties like good
allow easy drug release and encapsulation [187,188]. Hydrogels posi electrochemical behavior, patterning and good features to covalently
tioned (round window) near cochlea has efficiently delivered the neu link to substrates ensuring high adhesion features [202]. Such features
rotrophic factors and has proven more beneficial when positioned for a hydrogel offer a large voluminous space for biomolecules hence
within the scala tympani. The advantage of using RGD (Arginine-gly making PDMAAp/ PEDOT a promising candidate for drug delivery ap
cine-aspartic acid)-functionalized hydrogel provides better environment plications. Fluorescein (anionic dye) was investigated primarily as
hence supporting neuronal and tissue growth [189,190] hence this model drug showing release behavior governed by passive diffusion
property of hydrogels helps in improving neural regeneration process in smartly triggered by electrical stimulus. The detected quantity is more
a deteriorated cochlea. Thus CIs provide a good platform or an easy way than six times higher in comparison to that released from a conventional
to direct the hydrogel loaded with drugs into the cochlea. Employing PEDOT: PSS system. The conducting polymer hydrogel facilitates the
this principle Chikar and coworkers [191] have developed a active release of Dex, in comparison to the previously used PEDOT/Dex.
PEDOT-Arginine-glycine-aspartic acid (RGD)-Alginate functionalized It is suggested that PEDOT/PDMAAp is an interesting alternative for
hydrogel coating for release of neurotropic factors to the cochlear fluid conducting polymer based drug release systems, with the potential to
spaces of guinea pigs. The presence of PEDOT enables the electrode fluid offer more volume for storage, yet retaining the excellent electro
charge transfer hence acting as a good interface between tissues and chemical properties known for PEDOT electrodes [84]. Furthermore
(RGD)-functionalized alginate hydrogel thus helping to achieve the release study successfully performed on drug like Dex (anti-in
release of neurotrophic drugs consequently reducing the cochlear and flammatory) to study the potential of PDMAAp /PEDOT systems turns
auditory nerve degeneration. The PEDOT based functionalized alginate out to be very useful system in tuning the inflammatory responses eli
hydrogel coating for studying the effect on the cochlea was evaluated in cited by brain and other neural prosthetic devices.
an individual and mutual way for PEDOT/RGD functionalized alginate
18
4. Conclusion [11] J. Qu, X. Zhao, Y. Liang, Y. Xu, P.X. Ma, B. Guo, Degradable conductive injectable
hydrogels as novel anti-becterial,antioxidant wound dressings for wound healing,
Chem. Eng. J. 362 (2019) 548–560.
A quality about above mentioned pure PEDOT-PSS systems prepared [12] J. Liang, B. He, P. Yu, X. Zhao, H. Wu, J. Li, Y. Sun, Q. Fan, Facile construction of
by simply varying the experimental conditions gives a glimpse of an 3D magnetic graphene oxide hydrogel via incorporating assembly and chemical
experimentalist and their caliber to draw such a major difference in bubble and its application in arsenic remediation, Chem. Eng. J. 358 (2019)
552–563.
properties on a same system. Credit goes to the researchers whose efforts [13] Y. Wu, Y.X. Chen, J. Yan, D. Quinn, P. Dong, S.W. Sawyer, P. Soman, Fabrication
have proven fruitful and the resources have been fully utilized to deci of conductive gelatin methacrylate-polyaniline hydrogels, Acta Biomater. 33
pher the knowledge from a single system through different approaches. (2016) 122–130.
[14] J. LBredas, G.B. Street, Polarons, bipolarons, and solitons in conducting polymers,
PEDOT shares some important features like its versatile synthetic pro Acc. Chem. Res. 18 (1985) 309–315.
cedure, conductivity etc. which makes it a best commercially available [15] A. MacDiarmid, J. Chiang, A. Richter, A.J. Epstein, Polyaniline: a new concept in
materials for achieving the desired results. The PEDOT CPHs harbor conducting polymers, Synth. Met. 18 (1987) 285–290.
[16] A.G. MacDiarmid, Synthetic metals: a novel role for organic polymers (Nobel
enormous potential in divergent field of applications like bioelectronics lecture), Angew. Chem. Int. Ed. 40 (2001) 2581–2590.
biosensors and supercapacitor devices. In this review we have high [17] A.J. Hodgson, K. Gilmore, C. Small, G.G. Wallace, I.L. Mackenzie, T. Aoki,
lighted the role of solvent in tuning the conductivity of pure PEDOT:PSS N. Ogata, N. Reactive supramolecular assemblies of mucopolysaccharide,
polypyrrole and protein as controllable biocomposites for a new generation of
systems like the conductivity values could be measured as high as “intelligent biomaterials”, Supramol. Sci. 1 (1994) 77–83.
20 S cm− 1 in PBS (physiological conditions), 40 S cm− 1 in deionized [18] A.K. Gaharwar, N.A. Peppas, A. Khademhosseini, Nanocomposite hydrogels for
water and in 8.8 S cm-1 H2SO4. However there is still a large void biomedical applications, Biotechnol. Bioeng. 111 (2014) 441–453.
[19] S. Choi, S.I. Han, D. Kim, T. Hyeon, D.-H. Kim, High-performance stretchable
available for exploring PEDOT based hydrogel by functionalizing the
conductive nanocomposites: materials, processes, and device applications, Chem.
PEDOT CPH’s in such a manner so that we can produce tissue scaffolds Soc. Rev. (2018), https://doi.org/10.1039/C8CS00706C.
with tunable internal morphologies, high mechanical and swelling [20] S. Smart, A. Cassady, G. Lu, D. Martin, The biocompatibility of carbon nanotubes,
disposition which can ease their integration in electro-conductive tissues Carbon 44 (2006) 1034–1047.
[21] M. Hussain, M. Kabir, A. Sood, On the cytotoxicity of carbon nanotubes, Curr. Sci.
such as cardiac tissues. We have started working on PEDOT as con 96 (2009) 664–673.
ducting polymer in hydrogels that will enhance not only the conduc [22] Y. Wu, L. Wang, B. Guo, P.X. Ma, Interwoven aligned conductive nanofiber yarn/
tivity values of hydrogels but also can manipulate its field of application. hydrogel composite scaffolds for engineered 3D cardiac anisotropy, ACS Nano 11
(2017) 5646–5659.
This review further helps to describe the various strategies influencing [23] Y. Wu, L. Wang, B. Guo, Y. Shao, P.X. Ma, Electroactive biodegradable
the various properties of PEDOT hydrogels as such gives us a new ways polyurethane significantly enhanced Schwann cells myelin gene expression and
of thinking into challenging roles played effectively by PEDOT as con neurotrophin secretion for peripheral nerve tissue engineering, Biomaterials 87
(2016) 18–31.
ducting polymer in formulating large number of electro-conductive [24] M. Xie, L. Wang, B. Guo, Z. Wang, Y.E. Chen, P.X. Ma, Ductile electroactive
hydrogels for large number of desired applications such as tissue engi biodegradable hyperbranched polylactide copolymers enhancing myoblast
neering, micropatterning, drug delivery, bioelectronics etc. differentiation, Biomaterials 71 (2015) 158–167.
[25] L. Li, J. Ge, L. Wang, B. Guo, P.X. Ma, Electroactive nanofibrous biomimetic
scaffolds by thermally induced phase separation, J. Mater. Chem. B 2 (2014)
Declaration of Competing Interest 6119.
[26] A. Guiseppi-Elie, Electroconductive hydrogels: synthesis, characterization and
biomedical applications, Biomaterials 31 (2010) 2701–2716.
The authors declare that they have no known competing financial
[27] T.F. O’Connor, K.M. Rajan, A.D. Printz, D.J. Lipomi, Towards organic electronics
interests or personal relationships that could have appeared to influence with properties inspired by biological tissue, J. Mater. Chem. B 3 (2015)
the work reported in this paper. 4947–4952.
[28] K.H. Sun, Z. Liu, C.J. Liu, T. Yu, T. Shang, C. Huang, M. Zhou, C. Liu, F. Ran, Y. Li,
Y. Shi, L.J. Pan, Evaluation of in vitro and in vivo biocompatibility of a
Acknowledgement myoinositol hexakisphosphate gelated polyaniline hydrogel in a rat model, Sci.
Rep. 6 (2016) 23931.
Mushtaq A. Bhat and Reyaz A. Rather are thankful to TEQIP-III Is [29] G.V. Zozoulenko, A. Singh, S.K. Singh, V. Gueskine, X. Crispin, M. Berggren,
Polarons, bipolarons and absorption spectroscopy of PEDOT, ACS Appl. Polym.
lamic University of Science and Technology (IUST), Awantipora, J&k, Mater. 1 (2019) 83–94.
india for providing research fellowships and support for carrying out the [30] J. Stejskal, Conducting polymer hydrogels, Chem. Pap. 71 (2017) 269–291.
research. [31] D. Mawad, A. Lauto, G.G. Wallace, in: S. Kalia (Ed.), Conductive Polymer
Hydrogels in Polymeric Hydrogels as Smart Biomaterials, Springer International
Publishing, Cham, 2016, pp. 19–44.
References [32] Y. Ido, D. Takahashi, M. Sasaki, K. Nagamine, T. Miyake, P. Jasinski,
M. Nishizawa, Conducting polymer microelectrodes anchored to hydrogel films,
[1] A.G. Elie, Electroconductive hydrogels: synthesis, characterization and ACS Macro Lett. 1 (3) (2012) 400–403.
biomedical applications, Biomaterials 31 (2010) 2701–2716. [33] L. Pan, G. Yu, D. Zhai, H.R. Lee, W. Zhao, N. Liu, H. Wang, B.C.-K. Tee, Y. Shi,
[2] K. Yue, Synthesis, properties, and biomedical applications of gelatin methacryloyl Y. Cui, Z. Bao, Hierarchical nanostructured conducting polymer hydrogel with
(GelMA) hydrogels, Biomaterials 73 (2015) 254–271. high electrochemical activity, Proc. Nat. Acad. Sci. USA 109 (2012) 9287–9292.
[3] F. Ullah, M.B. Othman, F. Javed, Z. Ahmad, H.M. Akil, Classification, processing [34] A.S. Hoffman, Hydrogels for biomedical applications, Adv. Drug Deliv. Rev. 64
and application of hydrogels: a review, Mater. Sci. Eng. C 57 (2015) 414–433. (2002) 18–23.
[4] A.H. Shalla, Z. Yaseen, M.A. Bhat, T.A. Rangreez, M. Maswal, Recent review for [35] T. Kakuta, Y. Takashima, M. Nakahata, M. Otsubo, H. Yamaguchi, A. Harada,
removal of metal ions by hydrogels, Sep. Sci. Technol. 54 (2019) 89–100. Preorganise hydrogel: self-healing properties of supramolecular hydrogels formed
[5] A.H. Shalla, T.A. Rangreez, M.A. Rizvi, Z. Yaseen, Strength and sorption capacity by polymerization of Host-Guest-monomers that contain cyclodextrins and
modulation of carboxymethylcellulose hydrogels in presence of ester-bonded hydrophobic guest groups, Adv. Mater. 25 (2013) 2849–2853.
Gemini surfactants, J. Mol. Liq. 238 (2017) 215–224. [36] D.C. Tuncaboylu, M. Sari, W. Oppermann, O. Okay, Macromolecules, tough and
[6] A.H. Shalla, M.A. Bhat, Z. Yaseen, Hydrogels for removal of recalcitrant organic self-healing hydrogels formed via hydrophobic interactions, Macromolecules 44
dyes: a conceptual overview, J. Environ. Chem. Eng. 6 (2018) 5938–5949. (2011) 4997–5005.
[7] L.L. Palmese, R.K. Thapa, M.O. Sullivan, K.L. Kiick, Hybrid hydrogels for [37] M.A. Gonzalez, J.R. Simon, A. Ghoorchian, Z. Scholl, S. Lin, M. Rubinstein,
biomedical applications, Curr. Opin. Chem. Eng. 24 (2019) 143–157. P. Marszalek, A. Chilkoti, G.P. López, X. Zhao, Strong, tough, stretchable and self-
[8] Y. Wang, Z. Coa, J. Wu, C. Qiu, Y. Zhao, F. Shao, H. Wang, J. Zheng, G. Huang, adhesive hydrogels from intrinsically unstructured proteins, Adv. Mater. 29
Mechanically robust, ultrastrechable and thermal conducting composite (2017), 1604743.
hydrogels and its biomedical applications, Chem. Eng. J. 360 (2019) 231–242. [38] M. Liu, S. Wang, L. Jiang, Nature inspired superwettability systems, Nat. Rev.
[9] H. Fang, J. Wang, L. Li, L. Xu, Y. Wu, Y. Wang, X. Fei, J. Tian, Y. Li, A novel high Mater. 2 (2017) 17036.
Strength poly(ionic liquid)/PVA hydrogel dressing for antibacterial applications, [39] N. Baheiraei, Synthesis, characterization and antioxidant activity of a novel
Chem. Eng. J. 378 (2019), 122043. electroactive and biodegradable polyurethane for cardiac tissue engineering
[10] Y. Liang, M. Wang, Z. Zhang, G. Ren, Y. Liu, S. Wu, J. Shen, Facile synthesis of application, Mater. Sci. Eng. C Mater. 44 (2014) 24–37.
ZnO QDs@GO-CS hydrogel for synergetic antibacterial applications and [40] Q. Wang, Q. Wang, W. Teng, Injectable, degradable, electroactive nanocomposite
enhanced wound healing, Chem. Eng. J. 378 (2019), 122043. hydrogels containing conductive polymer nanoparticles for biomedical
applications, Int. J. Nanomed. 11 (2016) 131–144.
19
[41] B.L. Guo, L. Glavas, A.C. Albertsson, Biodegradable and electrically conducting [71] Q. Chen, H. Lu, F. Chen, L. Chen, N. Zhang, M. Ma, Supramolecular hydrogels for
polymers for biomedical applications, Prog. Polym. Sci. 38 (2013) 1263–1286. high-voltage and neutral-pH flexible supercapacitors, ACS Appl. Energy Mater. 1
[42] R.A. Green, R.T. Hassarati, J.A. Goding, S. Baek, N.H. Lovell, P.J. Martens, L.A. (8) (2018) 4261–4268.
P. Warren, Conductive hydrogels: mechanically robust hybrids for use as [72] Q. Wu, J. Wei, B. Xu, X. Liu, H. Wang, W. Wang, Q. Wang, W. Liu, A robust,
biomaterials, Macromol. Biosci. 12 (2012) 494–501. highly stretchable supramolecular polymer conductive hydrogel with self-
[43] S. Xu, L. Deng, J. Zhang, L. Yin, A. Dong, Composites of electrospun-fibers and healability and thermo-processability, Sci. Rep. 7 (2017) 41566.
hydrogels: a potential solution to current challenges in biological and biomedical [73] M.C.G. Saborio, S. Lazalaco, G. Fabregat, J. Puiggali, F. Estrany, C. Alman,
field, J. Biomed. Mater. Res. B Appl. Biomater. 104 (2016) 640–656. Flexible electrodes for supercapacitors based on the supramolecular assembly of
[44] A.J. Engler, S. Sen, H.L. Sweeney, D.E. Discher, Matrix elasticity directs stem cell biohydrogel and conducting polymer, J. Phys. Chem. C 122 (2018) 1078–1090.
lineage specification, Cell 126 (2006) 677–689. [74] M.Y. Teo, N. Ravichanran, N. Kim, S. Kee, L. Stuart, K.C. Aw, J. Stringer, Direct
[45] P. Humpolicek, V. Kasparkova, P. Saha, J. Stejskal, Biocompatibility of patterning of highly conductive PEDOT:PSS/ionic liquid hydrogel via
polyaniline, Synth. Met. 162 (2012) 722–727. microreactive inkjet printing, ACS Appl. Mater. Interfaces 11 (2019)
[46] L.C. Li, J. Ge, P.X. Ma, B.L. Guo, Injectable conducting interpenetrating polymer 37069–370761.
network hydrogels from gelatin-graft-polyaniline and oxidized dextran with [75] Z. Yang, J. Ma, B. Bia, A. Qui, D. Losic, D. Shi, M. Chen, Free-standing PEDOT/
enhanced mechanical properties, RSC Adv. 5 (2015) 92490–92498. polyaniline conductive polymer hydrogel for flexible solid-state supercapacitors,
[47] A.El-hady, Box PO Research article development of a novel conductive CMC Electrochim. Acta 322 (2019), 134769.
\polyaniline CMC polyaniline hydrogel Textile Chemistry and Technology, [76] Y. Ido, D. Takahashi, M. Sasaki, K. Nagamine, T. Miyake, P. Jasinski,
Scopus affiliation ID 60014618, 33EL Bohouthst, 2015. M. Nishizawa, Conducting polymer microelectrodes anchored to hydrogel films,
[48] L. Zhao, Z. Ma, Facile synthesis of polyaniline– polythionine redox hydrogel: ACS Macro Lett. 1 (3) (2012) 400–403.
conductive, antifouling and enzyme-linked material for ultrasensitive label-free [77] A.R. Spencer, A. Primbetov, A.N. Koppes, R.A. Koppes, H. Fenniri, N. Annabi,
amperometric immunosensor toward carcinoma antigen- 125, Anal. Chim. Acta Electroconductive gelatin methacryloyl-PEDOT:PSS composite hydrogels: design,
997 (2018) 60–66. synthesis, and properties, ACS Biomater. Sci. Eng. 4 (2018) 1558–1567.
[49] H. Al-Sagur, S. Komathi, M.A. Khan, A.G. Gurek, A. Hassan, A novel glucose [78] I.D. Agua, S. Marina, C. Pitsalidis, D. Mantione, M. Ferro, D. Iandolo, A.
sensor using lutetium phthalocyanine as redox mediator in reduced graphene S. Sanchez, G.G. Malliaris, R.M. Owens, Conducting polymer scaffolds based on
oxide conducting polymer multifunctional hydrogel, Biosens. Bioelectron. 92 poly(3,4-ethylenedioxythiophene) and Xathan Gum for Live-cell Monitoring, ACS
(2017) 638–645. Omega 3 (2018) 7424–7431.
[50] J. Das, P. Sarkar, Enzymatic electrochemical biosensor for urea with a polyaniline [79] D. Mawad, A.A. Schnirman, J. Tonkin, J. Ramos, S. Inal, M.M. Mahat, N. Darwish,
grafted conducting hydrogel composite modified electrode, RSC Adv. 6 (2016) L.Z. Dantsis, G.G. Mlaliaras, J.J. Gooding, A. Lauto, M.M. Stevens,
92520–92533. Electroconductive hydrogel based on functional poly(ethylenedioxy thiophene),
[51] A. Słoniewska, B. Pałys, Supramolecular polyaniline hydrogel as a support for Chem. Mater. 28 (2016) 6080–6088.
urease, Electrochim. Acta 126 (2014) 90–97. [80] H.Y. Gong, J. Park, W. Kim, J. Kim, J.Y. Lee, W.-G. Koh, A novel conductive and
[52] A. Jabłońska, B. Pałys, Effect of the polymerization bath on structure and micro-patterned PEG based hydrogel enabling the topographical and electrical
electrochemical properties of polyaniline-poly(styrene sulfonate) hydrogels, stimulation of myoblasts, ACS Appl. Mater. Interfaces 11 (2019) 47695–47706.
J. Electroanal. Chem. 784 (2017) 115–123. [81] Q. Wang, X. Pan, C. Lin, D. Lin, Y. Ni, L. Chen, L. Huang, S. Cao, X. Ma,
[53] S. Hosseinzadeh, S.M. Rezayat, E. Vashegani-Farahani, M. Mahmoudifard, Biocompatible, self-wrinkled, antifreezing and stretchable hydrogel-based
S. Zamanlui, M. Soleimani, Nanofibrous hydrogel with stable electrical wearable sensor with PEDOT:sulfonated lignin as conductive materials, Chem.
conductivity for biological applications, Polymer 97 (2016) 205–216. Eng. J. 370 (2019) 1039–1047.
[54] S. Khorshidi, A. Karkhaneh, Hydrogel/fiber conductive scaffold for bone tissue [82] Y. Xu, X. Ynag, A.K. Thomas, P.A. Patsis, T. Kurth, M. Kraeter, K. Eckert,
engineering, J. Biomed. Mater. Res. Part A 106 (2018) 718–724. M. Bornhauser, Y. Zhang, Non-covalently assembled electroconductive hydrogel,
[55] D. Xu, L. Fan, L. Gao, Y. Xiong, Y. Wang, Q. Ye, A. Yu, H. Dai, Y. Yin, J. Cai, ACS Appl. Mater. Interfaces 10 (17) (2018) 14418–14425.
L. Zhang al, Micro-nanostructured polyaniline assembled in cellulose matrix via [83] Y. Xu, M. Cui, P.A. Patsis, M. Gunther, X. Yang, K. Eckert, Y. Zhnag, Reversibly
interfacial polymerization for applications in nerve regeneration, ACS Appl. assembled electroconductive hydrogel via host-guest interaction for 3D cell
Mater. Interfaces 8 (2016) 17090–17097. culture, ACS Appl. Mater. Interfaces 11 (2019) 7715–7725.
[56] C.J. Pérez-Martínez, S.D. Morales Chávez, T. Del Castillo-Castro, T.E. Lara [84] C. Kleber, K. Liekamp, J. Rihe, M. Asplund, Electrochemically controlled drug
Ceniceros, M.M. Castillo-Ortega, D.E. Rodríguez-Félix, J.C. Gálvez Ruiz, release from a conducting polymer hydrogel (PDMAAp/PEDOT) for local therapy
Electroconductive nanocomposite hydrogel for pulsatile drug release, React. and bioelectronics, Adv. Healthc. Mater. 8 (10) (2019), 1801488.
Funct. Polym. 100 (2016) 12–17. [85] N. Paradee, A. Sirivat, Electrically controlled release of benzoic acid from poly
[57] B. Tasdelen, Conducting hydrogels based on semi-interpenetrating networks of (3,4-ethylenedioxythiophene)/alginate matrix: effect of conductive poly(3,4-
polyaniline in poly(acrylamide- co-itaconic acid) matrix: synthesis and ethylenedioxythiophene) Morphology, J. Phys. Chem. B 118 (2014) 9263–9271.
characterization, Polym. Adv. Technol. 28 (2017) 1865–1871. [86] L.S.M. Teixeira, J. Patterson, F. Pluyten, Skeletal tissue regeneration: where can
[58] L.B.J. da Silva, R.L. Oréfice, Synthesis and electromechanical actuation of a hydrogels play a role? Int. Orthop. 38 (2014) 1861–1876.
temperature, pH, and electrically responsive hydrogel, J. Polym. Res. 21 (2014) [87] C.N. Kotanen, The effect of the physicochemical properties of bioactive
466–1–466–469. electroconductive hydrogels on the growth and proliferation of attachment
[59] R. Hu, J. Zhao, R. Jiang, J. Zheng, Preparation of high strain polyaniline/ dependent cells, Biomaterials 34 (2013) 6318–6327.
polyvinyl alcohol composite and its applications in stretchable supercapacitor, [88] D. Mawad, A. Single, Component conducting polymer hydrogel as a scaffold for
J. Mater. Sci. Mater. Electron. 28 (2017) 14568–14574. tissue engineering, Adv. Funct. Mater. 22 (2012) 2692–2699.
[60] R. Huang, Y. Guo, Z. Chen, X. Zhang, J. Wang, B. Yang, An easy and scalable [89] Y. Shi, L. Peng, G. Yu, Nanostructured conducting polymer hydrogels for energy
approach to synthesize three-dimensional sandwich-like Si/ polyaniline/ storage applications, Nanoscale 7 (2015) 12796–12806.
graphene nano-architecture anode for lithium ion batteries, Ceram. Int. 4 (2018) [90] Y. Shi, C. Ma, L. Peng, G. Yu, Conductive “smart” hybrid hydrogels with PNIPAM
4282–4286. and nanostructured conductive polymers, Adv. Funct. Mater. 25 (2015)
[61] Y. Luo, Q. Zhang, W. Hong, Z. Xiao, H. Bai, A high-performance electrochemical 1219–1225.
supercapacitor based on a polyaniline/reduced graphene oxide electrode and a [91] M.R. Abidian, D.C. Martin, Multifunctional nanobiomaterials for neural
copper (ii) ion active electrolyte, Phys. Chem. Chem. Phys. 20 (2018) 131–136. interfaces, Adv. Funct. Mater. 19 (2009) 573–585.
[62] N. Suganya, V. Jaisankar, E.K. TSivakumar, Conducting polymeric hydrogel [92] T. Dai, X. Qing, Y. Lu, Y. Xia, Conducting hydrogels with enhanced mechanical
electrolyte based on carboxymethylcellulose and polyacrylamide/polyaniline for strength, Polymer 50 (2009) 5236–5241.
supercapacitor applications, Int. J. Nanosci. 17 (2017), 1760003. [93] B.C. Kim, G.M. Spinks, G.G. Wallace, R. John, Electro-formation of conducting
[63] H. Guo, W. He, Y. Lu, X. Zhang, Self-crosslinked polyaniline hydrogel electrodes polymers in hydrogel support matrix, Polymer 41 (2000) 1783–1790.
for electrochemical energy storage, Carbon 92 (2015) 133–141. [94] S. Ghosh, J. Rasmusson, O. Inganas, Conductivity in conjugated polymer blends:
[64] M. Smirnov, M. Sokolova, N.V. Bobrova, I.A. Kasatkin, E. Lahderanta, G. Ionic crosslinking in blends of poly(3,4-ethylenedioxythiophene) poly
K. Elyashevich, Capacitance properties and structure of (styrenesulfonate) and poly(vinylpyrrolidone), Adv. Mater. 10 (1998)
electroconductinghydrogels based on copoly(aniline-P-phenylenediamine) and 1097–1099.
polyacrylamide, J. Power Sources 304 (2016) 102–110. [95] N. Mano, J.E. Yoo, J. Tarver, Y.-L. Loo, A. Heller, An electron-conducting cross-
[65] M. Moussa, Z. Zhao, M.F. El-Kady, H. Liu, A. Michelmore, N. Kawashima, linked polyaniline-based redox hydrogel, formed in one step at pH 7.2, wires
P. Majewski, J. Ma, Free-standing composite hydrogel films for superior glucose oxidase, J. Am. Chem. Soc. 129 (2007) 7006–7007.
volumetric capacitance, J. Mater. Chem. A 3 (2015) 15668–15674. [96] T. Dai, Y. Jia, Supramolecular hydrogels of polyaniline-poly(styrene sulfonate)
[66] P. Li, S. Yuan, Q. Tang, B. He, Robust conducting gel electrolytes for efficient prepared in concentrated solutions, Polymer 52 (2011) 2550–2558.
quasi-solid-state dye-sensitized solar cells, Electrochim. Acta 137 (2014) 57–64. [97] T. Dai, X. Qing, Y. Lu, Y. Xia, Conducting hydrogels with enhanced mechanical
[67] S. Yuan, Q. Tang, B. He, L. Yu, Conducting gel electrolytes with microporous strength, Polymer 50 (2009) 5236–5241.
structures for efficient quasisolid- state dye-sensitized solar cells, J. Power [98] S.K. Siddhanta, R. Gangopadhyay, Conducting polymer gel formation of a novel
Sources 273 (2015) 1148–1155. semi-IPN from polyaniline and crosslinked poly(2-acrylamido-2-methyl
[68] Y. Xia, H. Zhu, Polyaniline nanofiber-reinforced conducting hydrogel with unique propanesulphonic acid), Polymer 46 (2005) 2993–3000.
pH-sensitivity, Soft Matter 7 (2011) 9388–9393. [99] S.K. Siddhanta, R. Gangopadhyay, Conducting polymer gel: formation of a novel
[69] B. Yao, H. Wang, Q. Zhoa, M. Wu, M. Zhnag, C. Li, G. Shi, Ultrahigh-conductivity semi-IPN from polyaniline and crosslinked poly(2-acrylamido-2-methyl
polymer hydrogels with arbitrary structures, Adv. Mater. 29 (2017), 1700974. propanesulphonicacid), Polymer 46 (2005) 2993–3000.
[70] B. Lu, H. Yuk, S. Lin, N. Jian, K. Qu, J. Xu, X. Zhao, Pure PEDOT:PSS hydrogels,
Nat. Commun. 10 (2019) 1043.
20
[100] Q. Tang, J. Lin, J. Wu, C. Zhang, S. Hao, S, Two-steps synthesis of a poly [127] Y.Y. Lee, H.-Y. Kang, S.H. Gwon, G.M. Choi, S.-M. Lim, J.-Y. Sun, Y.-C. Joo,
(acrylate–aniline) conducting hydrogel with an interpenetrated networks A strain-insensitive stretchable electronic conductor: PEDOT: PSS/acrylamide
structure, Carbohydr. Polym. 67 (2007) 332–336. organogels, Adv. Mater. 28 (2016) 1636–1643.
[101] A. Srinivasan, J. Roche, V. Ravaine, A. Kuhn, Synthesis of conducting asymmetric [128] H. Warren, M.I.H. Panhuis, Electrically conducting PEDOT:PSS—gellan gum
hydrogel particles showing autonomous motion, Soft Matter 11 (2015) hydrogels, MRS Proc. 1569 (2013) 219–223.
3958–3962. [129] J. Goding, A. Gilmour, P. Martens, L. Poole-Warren, R. Green, Interpenetrating
[102] A.K. Bajpai, J. Bajpai, S.N. Soni, Designing polyaniline (PANI) and polyvinyl conducting hydrogel materials for neural interfacing electrodes, Adv. Healthc.
alcohol (PVA) based electrically conductive nanocomposites: preparation, Mater. 6 (2017), 1601177.
characterization and blood compatible study, J. Macromol. Sci. Part A 46 (2009) [130] A.G.Bayer, Eur. Patent 440 957, 1991, Agfa Gevaert, Eur. Patent 564, 1993, 911.
774–782. [131] S. Kirchmeyer, K. Reuter, Scientific importance, properties and growing
[103] Q. Li, J. Wu, Z. Tang, Y. Xiao, M. Huang, J. Lin, Application of poly(acrylic acid-g- applications of poly (3, 4-ethylenedioxythiophene), J. Mater. Chem. 15 (2005)
gelatin)/polypyrrole gel electrolyte in flexible quasi-solid-state dye-sensitized 2077.
solar cell, Electrochim. Acta 55 (2010) 2777–2781. [132] L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik, J.R. Reynolds, Poly (3,
[104] S. Zhou, M. Wang, X. Chen, F. Xu, Facile template synthesis of microfibrillated 4–ethylenedioxythiophene) and its derivatives: past, present, and future, Adv.
cellulose/polypyrrole/silver nanoparticles hybrid aerogels with electrical Mater. 12 (2000) 481–494.
conductive and pressure responsive properties, ACS Sustain. Chem. Eng. 3 (2015) [133] H.-E. Yin, F.-H. Huang, W.-Y. Chin, Hydrophobic and flexible conductive films
3346–3354. consisting of PEDOT: PSS-PBA/fluorine-modified silica and their performance in
[105] T. Dai, X. Qing, H. Zhou, C. Shen, J. Wang, Y. Lu, Mechanically strong conducting weather stability, J. Mater. Chem. 22 (2012) 14042.
hydrogels with special double-network structure, Synth. Met. 160 (2010) [134] R.W. Heuer, R. Wehermann, S. Kirchmeyer, Electrochromic window based on
791–796. conducting poly(3,4–ethylenedioxythiophene)–poly(styrene sulfonate), Adv.
[106] G.L. Mario Cheong, K.S. Lim, A. Jakubowicz, P.J. Martens, L.A. Poole-Warren, R. Funct. Mater. 12 (2002) 89–94.
A. Green, Conductive hydrogels with tailored bioactivity for implantable [135] 〈http://www.conductive-polymer.com/orgacon-conductiveinks%20html〉.
electrode coatings, Acta Biomater. 10 (2014) 1216–1226. [136] F. Jonas, W. Crafft, B. Muys, Poly(3, 4-ethylenedioxythiophene): Conductive
[107] M. Sasaki, B.B. Karikkineth, K. Nagamine, H. Kaji, K. Torimitsu, M. Nishizawa, coatings, technical applications and properties, Macromol. Symp. 100 (1995)
Highly conductive stretchable and biocompatible electrode-hydrogel hybrids for 169–173.
advanced tissue engineering, Adv. Healthc. Mater. 3 (2014) 1919–1927. [137] M.-A. De Paoli, G. Casalbore-Miceli, E.M. Girotto, W.A. Gazotti, All polymeric
[108] M. Karbarz, M. Gniadek, M. Donten, Z. Stojek, Intra-channel modification of solid state electrochromic devices, Electrochim. Acta 44 (1999) 2983–2991.
environmentally sensitive poly(N-isopropylacrylamide) hydrogel with polyaniline [138] Y. Cao, G. Yu, C. Zhang, R. Menon, A.J. Heeger, Synthetic metals polymer light-
using interphase synthesis, Electrochem. Commun. 13 (2011) 714–718. emitting diodes with polyethylene dioxythiophene–polystyrene sulfonate as the
[109] Y. Wu, Y.X. Chen, J. Yan, S. Yang, P. Dong, P. Soman, Fabrication of conductive transparent anode 87, 1997, pp. 171.
polyaniline hydrogel using porogen leaching and projection [139] J. Ouyang, C.-W. Chu, F.-C. Chen, Q. Xu, Y. Yang, High-conductivity poly
microstereolithography, J. Mater. Chem. B 3 (2015) 5352–5360. (3,4–ethylenedioxythiophene): poly(styrene sulfonate) film and its application in
[110] Y. Tao, J.X. Zhao, C.X. Wu, Polyacrylamide hydrogels with trapped sulfonated polymer optoelectronic devices, Adv. Funct. Mater. 15 (2005) 203–208.
polyaniline, Eur. Polym. J. 41 (2005) 1342–1349. [140] Y. Yoshika, G.E. Jabbour, Desktop inkjet printer as a tool to print conducting
[111] L.E. Valencia, C.J. Pérez Martínez, T. del Castillo Castro, M.M. Castillo Ortega, J. polymers, Synth. Met. 156 (2006) 779–783.
C. Encinas, Chemical polymerization of pyrrole in the presence of L-serine or L- [141] R. Kroon, D.A. Mengistie, D. Kiefer, J. Hynynen, J.D. Ryan, L. Yu, C. Müller,
glutamic acid: electrically controlled amoxicillin release from composite Thermoelectric plastics: from design to synthesis, processing and
hydrogel, J. Appl. Polym. Sci. 132 (2015). structure–property relationships, Chem. Soc. Rev. 45 (2016) 6147–6164.
[112] Y.-Y. Lee, H.-Y. Kang, S.H. Gwon, G.M. Choi, S.-M. Lim, J.-Y. Sun, Y. Joo, A strain- [142] D. Mantione, I. del Agua, A. Sanchez-Sanchez, D. Mecerreyes, Poly(3,4-
insensitive stretchable electronic conductor: PEDOT:PSS/acrylamide organogels, ethylenedioxythiophene) (PEDOT) derivatives: innovative conductive polymers
Adv. Mater. 28 (2016) 1636–1643. for bioelectronics, Polymers 9 (2017) 354.
[113] S. Brahim, D. Narinesingh, A. G-Elie, Synthesis and hydration properties of pH- [143] L.K. Povlich, J.C. Cho, M.K. Leach, J.M. Corey, J. Kim, D.C. Martin, Synthesis,
sensitive p(HEMA)-based hydrogels containing 3-(trimethoxysilyl) propyl copolymerization and peptide-modification of carboxylic acid-functionalized 3,4
methyacrylate, Biomacromolecules 4 (2003) 497–503. ethylenedioxythiophene (EDOTacid) for neural electrode interfaces, Biochim.
[114] F.A. Aouada, M.R. Guilherme, G.M. Campese, E.M. Girotto, A.F. Rubira, E. Biophys. Acta Gen. Subj. 2013 (1830) 4288–4293.
C. Muniz, Electrochemical and mechanical properties of hydrogels based on [144] B. Zhu, S.-C. Luo, H. Zhao, H.-A. Lin, J. Sekine, A. Nakao, C. Chen, Y. Yamashita,
conductive poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) and PAAm, H.-h Yu, Large enhancement in neurite outgrowth on a cell membrane-mimicking
Polym. Test. 25 (2006) 158–165. conducting polymer, Nat. Commun. 5 (2014) 4523.
[115] A. Tiwari, S.Q. Gong, Electrochemical synthesis of chitosan-co-polyaniline/ [145] L. Huang, J. Hu, L. Lang, X. Wang, P. Zhang, X. Jing, X. Wang, X. Chen, P.I. Lelkes,
WO3⋅nH2O composite electrode for amperometric detection of NO2 gas, A.G. MacDiarmid, Synthesis and characterization of electroactive and
Electroanalysis 20 (2008) 1775–1781. biodegradable ABA block copolymer of polylactide and aniline pentamer,
[116] F. Vidal, C. Plesse, P.H. Aubert, L. Beouch, F. Tran-Van, G. Palaprat, P. Verge, Biomaterials 28 (2007) 1741–1751.
P. Yammine, J. Citerin, A. Kheddar, L. Sauques, C. Chevrot, D. Teyssie, Poly(3,4- [146] H.-j Wang, L.-w Ji, D.-f Li, J.-Y. Wang, Characterization of nanostructure and cell
Ethylenedioxythiophene)-containing semi-interpenetrating polymer networks: a compatibility of polyaniline films with different dopant acids, J. Phys. Chem. B
versatile concept for the design of optical or mechanical electroactive devices, 112 (2008) 2671–2677.
Polym. Int. 59 (2010) 313–320. [147] P. Bober, P. Humpolíček, J. Pacherník, J. Stejskal, T. Lindfors, Conducting
[117] R. Balint, N.J. Cassidy, S.H. Cartmell, Conductive polymers: towards a smart polyaniline based cell culture substrate for embryonic stem cells and embryoid
biomaterial for tissue engineering, Acta Biomater. 10 (2014) 2341–2353. bodies, RSC Adv. 5 (2015) 50328–50335.
[118] J.Y. Kim, M.H. Kwon, Y.K. Min, S.K. Won, D.W. Ihm, Self- assembly and [148] A.C. Dasilva, A.T.S. Semeano, A.H.B. Dourado, H. Ulrich, Susana, C.D. Torresi,
crystalline growth of poly(3,4-ethylenedioxythiophene) nanofilms, Adv. Mater. Novel conducting and biodegradable copolymers with non-cytotoxic properties
19 (2007) 3501–3506. toward embryonic stem cells, ACS Omega 3 (2018) 5593–5604.
[119] J.M. D’Arcy, M.F. El-Kady, P.P. Khine, L. Zhang, S.H. Lee, N.R. Davis, D.S. Liu, M. [149] N. Batisse, E. R-Piñero, A self-standing hydrogel neutral electrolyte for high
T. Yeung, S.Y. Kim, C.L. Turner, A.T. Lech, P.T. Hammond, R.B. Kaner, Vapor- voltage and safe flexible supercapacitors, J. Power Sources 348 (2017) 168–174.
phase polymerization of nanofibrillar poly(3,4-ethylenedioxythiophene) for [150] E. Armelin, M.M. Pérez-Madrigal, C. Alemán, D.D. Díaz, Current status and
supercapacitors, ACS Nano 8 (2014) 1500–1510. challenges of biohydrogels for applications as supercapacitors and secondary
[120] M.N. Gueye, A. Carella, N. Massonnet, E. Yvenou, S. Brenet, J. Faure-Vincent, batteries, J. Mater. Chem. A 4 (2016) 8952–8968.
S. Pouget, F. Rieutord, H. Okuno, A. Benayad, R. Demadrille, Structure and [151] J. Bae, M.K. Song, Y.J. Park, J.M. Kim, M.L. Liu, Z.L. Wang, Fiber supercapacitors
dopant engineering in PEDOT thin films: practical tools for a dramatic made of nanowire-fiber hybrid structures for wearable/flexible energy storage,
conductivity enhancement, Chem. Mater. 28 (10) (2016) 3462–3468. Angew. Chem. Int. Ed. 50 (2011) 1683–1687.
[121] B. Cho, K.S. Park, J. Baek, H.S. Oh, Y.E. Koo, M.M. Lee, Single-crystal poly (3, 4- [152] Y.P. Fu, X. Cai, H.W. Wu, Z.B. Lv, S.C. Hou, M. Peng, X. Yu, D.C. Zou, Fiber
ethylenedioxythiophene) nanowires with ultrahigh conductivity, Nano Lett. 14 supercapacitors utilizing pen ink for flexible/wearable energy storage, Adv.
(6) (2014) 3321–3327. Mater. 24 (2012) 5713–5718.
[122] I. Shown, A. Ganguly, L.-C. Chen, K.-H. Chen, Conducting polymer-based flexible [153] J.E. McCarthy, C.A. Hanley, L.J. Brennan, V.G. Lambertini, Y.K. Gunko,
supercapacitor, Energy Sci. Eng. 3 (2015) 2–26. Fabrication of highly transparent and conducting PEDOT:PSS films using a formic
[123] Q. Wei, M. Mukaida, K. Kirihara, Y. Naitoh, T. Ishida, Recent progress on PEDOT acid treatment, J. Mater. Chem. C 2 (2014) 764–770.
based thermoelectric materials, Materials 8 (2015) 732–750. [154] D.S. Yu, K. Goh, H. Wang, L. Wei, W.C. Jiang, Q. Zhang, L.M. Dai, Y. Chen,
[124] A. Elschner, S. Kirchmeyer, W. Lövenich, U. Merker, K. Reuter, PEDOT: Principles Scalable synthesis of hierarchically structured carbon nano-tube–graphene fibres
and Applications of an Intrinsically Conductive Polymer, CRC Press, Boca Raton, for capacitive energy storage, Nat. Nanotechnol. 9 (2014) 555–562.
FL, USA, 2010. [155] G.X. Qu, J.L. Cheng, X.D. Li, D. Yuan, P.N. Chen, X. Chen, B. Wang, H.S. Peng,
[125] H. Yuk, B. Lu, X. Zhao, Hydrogel bioelectronics, Chem. Soc. Rev. 48 (2019) A fiber supercapacitor with high energy density based on hollow graphene/
1642–1667. conducting polymer fiber electrode, Adv. Mater. 28 (2016) 3646–3652.
[126] V.R. Feig, H. Tran, M. Lee, Z. Bao, Mechanically tunable conductive [156] L. Kou, T.Q. Huang, B.N. Zheng, Y. Han, X.L. Zhao, K. Gopalsamy, H.Y. Sun,
interpenetrating network hydrogels that mimic the elastic moduli of biological C. Gao, Coaxial wet-spun yarn supercapacitors for high-energy density and safe
tissue, Nat. Commun. 9 (2018) 2740. wearable electronics, Nat. Commun. 5 (2014) 3754.
21
[157] V.T. Le, H. Kim, A. Ghosh, J. Kim, J. Chang, Q.A. Vu, D.T. Pham, J.H. Lee, S. [180] X. Yu, S. Chung, D.Y. Chen, S.M. Wang, S.J. Dodd, J.R. Walters, J.T.R. Isaac, A.
W. Kim, Y.H. Lee, Coaxial fiber supercapacitor using all carbon material P. Koretsky, Thalamocortical inputs show postcritical- period plasticity, Neuron
electrodes, ACS Nano 7 (2013) 5940–5947. 74 (2012) 731–742.
[158] Y.J. Xia, J.Y. Ouyang, Significant conductivity enhancement of conductive poly [181] W.C. Huang, Y.C. Lo, Y.Y. Chen, S.Y. Chen, Neural interfaces with electrically
(3,4-ethylenedioxythiophene): poly(styrenesulfonate) films through a treatment controllable delivery of manganese ions applied for MEMRI functionalized deep
with organic carboxylic acids and inorganic acids, ACS Appl. Mater. Interfaces 2 brain stimulation, J. Control. Release 213 (2015) e112–e113.
(2010) 474–483. [182] R.A. Green, N.H. Lovell, G.G. Wallace, L.A. Poole-Warren, Conducting polymers
[159] Y.X. Xu, K.X. Sheng, C. Li, G.Q. Shi, Self-assembled graphene hydrogel via a one- for neural interfaces: challenges in developing an effective long-term implant,
step hydrothermal process, ACS Nano 4 (2010) 4324–4330. Biomaterials 29 (2008) 3393–3399.
[160] J.Y. Ouyang, Q.F. Xu, C.W. Chu, Y. Yang, G. Li, J. Shinar, On the mechanism of [183] R.T. Richardson, A.K. Wise, B.C. Thompson, B.O. Flynn, P.J. Atkinson, N.
conductivity enhancement in poly(3,4-ethylenedioxythiophene): poly(styrene J. Fretwell, J.B. Fallon, G.G. Wallace, R.K. Shepherd, G.M. Clark, Polypyrrole-
sulfonate) film through solvent treatment, Polymer 45 (2004) 8443–8450. coated electrodes for the delivery of charge and neurotrophins to cochlear
[161] J.E. McCarthy, C.A. Hanley, L.J. Brennan, V.G. Lambertini, Y.K. Gun’ko, neurons, Biomaterials 30 (2009) 2614–2624.
Fabrication of highly transparent and conducting PEDOT: PSS films using a formic [184] X. Cui, V.A. Lee, Y. Raphael, J.A. Wiler, J.F. Hetke, D.J. Anderson, D.C. Martin,
acid treatment, J. Mater. Chem. A 2 (2014) 764. Surface modification of neural recording electrodes with conducting polymer/
[162] D. Xu, X. Feng, X. Zhu, Y. Song, PEDOT: PSS hydrogel film for supercapacitors via biomolecule blends, J. Biomed. Mater. Res. 56 (2) (2001) 261–272.
AlCl3-induced cross-linking and subsequent organic solvent treatments, Mater. [185] K.A. Ludwig, J.D. Uram, J. Yang, D.C. Martin, D.R. Kipke, Chronic neural
Today Commun. 24 (2020), 101090. recordings using silicon microelectrode arrays electrochemically deposited with a
[163] C.C. Yu, C.Y. Wang, X. Liu, X.T. Jia, S. Naficy, K. Shu, M. Forsyth, G. Wallace, poly(3,4-ethylenedioxythiophene) (PEDOT) film, J. Neural Eng. 3 (1) (2006)
A cytocompatible robust hybrid conducting polymer hydrogel for use in a 59–70.
magnesium battery, Adv. Mater. 28 (2016) 9349–9355. [186] J.F. Mano, G.A. Silva, H.S. Azevedo, P.B. Malafaya, R.A. Sousa, S.S. Silva, L.
[164] J.Y. Ouyang, Recent advances of intrinsically conductive polymers, Acta Phys. F. Boesel, J.M. Oliveira, T.C. Santos, A.P. Marques, N.M. Neves, R.L. Reis, Natural
Chim. Sin. 34 (2018) 1211–1220. origin biodegradable systems in tissue engineering and regenerative medicine:
[165] D. Kim, J. Kim, Y. Ko, K. Shim, J.H. Kim, J. You, A facile approach for present status and some moving trends, J. R. Soc. Interface 4 (17) (2007)
constructing conductive polymer patterns for application in electrochromic 999–1030.
devices and flexible microelectrodes, ACS Appl. Mater. Interfaces 8 (2016) [187] J.L. Hendricks, J.A. Chikar, M.A. Crumling, Y. Raphael, D.C. Martin, Localized
33175–33182. cell and drug delivery for auditory prostheses, Hear. Res. 242 (2008) 117–131.
[166] V.R. Feig, H. Tran, M. Lee, K. Liu, Z. Huang, L. Beker, D.G. Mackanic, Z. Bao, An [188] T. Coviello, P. Matricardi, F. Alhaique, Drug delivery strategies using
electrochemical gelation method for patterning conductive PEDOT:PSS polysaccharidic gels, Expert Opin. Drug Deliv. 3 (3) (2006) 395–404.
hydrogels, Adv. Mater. 31 (2019), 1902869. [189] J.L. Drury, D.J. Mooney, Hydrogels for tissue engineering: scaffold design
[167] S. Hong, D. Sycks, H.F. Chan, S. Lin, G.P. Lopez, F. Guilak, K.W. Leong, X. Zhao, variables and applications, Biomaterials 24 (2003) 4337–4351.
3D printing of highly stretchable and tough hydrogels into complex, cellularized [190] J.S. Katz, J.A. Burdick, Hydrogel mediated delivery of trophic factors for neural
structures, Adv. Mater. 27 (2015) 4035–4040. repair, Wiley Interdiscip. Rev. Nanomed. Nanobiotechnol. 1 (2009) 128–139.
[168] T.J. Hinton, Q. Jallerat, R.N. Palchesko, J.H. Park, M.S. Grodzicki, H.-J. Shue, M. [191] J.A. Chikar, J.L. Hendricks, S.M. Richardson-Burns, Y. Raphael, B.E. Pfingst, D.
H. Ramadan, A.R. Hudson, A.W. Feinberg, Three-dimensional printing of complex C. Martin, The use of a dual PEDOT and RGD-functionalized alginate hydrogel
biological structures by freeform reversible embedding of suspended hydrogels, coating to provide sustained drug delivery and improved cochlear implant
Sci. Adv. 1 (2015), e1500758. function, Biomaterials 33 (2012) 1982–1990.
[169] S. Sakine, Y. Ido, T. Miyake, K. Nagamine, M. Nishizawa, Conducting polymer [192] Y. Raphael, D.J. Colesa, C.-C. Lee, R. Minoda, T. Nakaizumi, B.E.P. Fingst,
electrodes printed on hydrogel, J. Am. Chem. Soc. 132 (38) (2010) 13174–13175. Postdeafening treatment of the mature cochlea by upregulation of BDNF:
[170] L. Lin, Q. Tang, J. Wu, Q. Li, A multifunctional hydrogel with high-conductivity, Histological and functional effects. Association for Research in Otolaryngology,
pH-responsive, and release properties from polyacrylate/polyptrrole, J. Appl. MidWinter Meeting, Daytona Beach, FL, 2004.
Polym. Sci. 116 (2010) 1376–1383. [193] B. Fritzsch, L. Tessarollo, E. Coppola, L.F. Reichardt, Neurotrophins in the ear:
[171] Q. Tang, J. Wu, H. Sun, J. Lin, S. Fan, D. Hu, Polyaniline/polyacrylamide their roles in sensory neuron survival and fiber guidance, Prog. Brain Res. 146
conducting composite hydrogel with a porous structure, Carbohydr. Polym. 74 (2004) 265–278.
(2008) 215–219. [194] I. Fariñas, K.R. Jones, L. Tessarollo, A.J. Vigers, E. Huang, M. Kirstein, D.C. de
[172] S. Naficy, J.M. Razal, G.M. Spinks, G.G. Wllace, P.G. Whitten, Electrically Caprona, V. Coppola, C. Backus, L.F. Reichardt, B. Fritzsch, Spatial shaping of
conductive, tough hydrogels with pH sensitivity, Chem. Mater. 24 (2012) cochlear innervation by temporally regulated neurotrophin expression,
3425–3433. J. Neurosci. 21 (16) (2001) 6170–6180.
[173] S. Ghosh, J. Rasmusson, O. Inganäs, Supramolecular self-assembly for enhanced [195] B. Fritzsch, U. Pirvola, J. Ylikoski, Making and breaking the innervation of the
conductivity in conjugated polymer blends: ionic crosslinking in blends of poly ear: neurotrophic support during ear development and its clinical implications,
(3,4-ethylenedioxythiophene)-poly(styrenesulphonate) and poly Cell Tissue Res. 295 (1999) 369–382.
(vinylpyrrolidone), Adv. Mater. 10 (14) (1998) 1097–1099. [196] J.M. Miller, D.H. Chi, L.J. O’Keeffe, P. Kruszka, Y. Raphael, R.A. Altschuler,
[174] S. Ghosh, O. Inganäs, Conducting polymer hydrogels as 3D electrodes: application Neurotrophins can enhance spiral ganglion cell survival after inner hair cell loss,
for supercapacitors, Adv. Mater. 11 (14) (1999) 1214–1218. Int. J. Dev. Neurosci. 15 (1997) 631–643.
[175] T. Dai, X. Jiang, S. Hua, X. Wang, Y. Lu, Facile fabrication of conducting polymer [197] H. Staecker, R. Kopke, B. Malgrange, P. Lefebvre, T.R. Van de Water, NT-3 and/or
hydrogel via supramolecular self-assembly, Chem. Commun. 36 (2008) BDNF therapy prevents loss of auditory neurons following loss of hair cells,
4279–4281. Neuroreport 7 (1996) 889–894.
[176] T. Dai, Z. Shi, C. Shen, J. Wang, Y. Lu, Self-strengthened conducting polymer [198] L.M. Lira, S.I.C. de Torresi, Conducting polymer–hydrogel composites for
hydrogel, Synth. Met. 160 (2010) 1101–1106. electrochemical release devices: synthesis and characterization of semi-
[177] L. Jiang, C. Gentile, A. Lauto, C. Cui, Y. Song, T. Romeo, S.M. Silva, O. Tang, interpenetrating polyaniline–polyacrylamide networks, Electrochem. Commun. 7
P. Sharma, G. Figtree, J.J. Gooding, D. Mawad, Versatile fabrication approach of (2005) 717–723.
conductive hydrogels via copolymerization with vinyl monomers, ACS Appl. [199] A.W. Bridges, A.J. Garcia, Anti-inflammatory polymeric coatings for implantable
Mater. Interfaces 9 (2017) 44124–44133. biomaterials and devices, J. Diabetes Sci. Technol. 2 (2008) 984–994.
[178] Y.F. Zhang, M.M. Guo, Y. Zhang, C.Y. Tang, C. Jiang, Y Dong, W.C. Law, F.P Du, [200] L. Poole-Warren, J. Goding, R. Green, P. Martens, Challenges of therapeutic
Flexible, stretchable and conductive PVA/PEDOT:PSS composite hydrogels delivery using conducting polymers, Ther. Deliv. 3 (2012) 421–427.
prepared by SIPN strategy, Polym. Test. 81 (2020), 106213. [201] R.A. Green, S. Baek, L.A. Poole-Warren, P.J. Martens, Conducting polymer-
[179] X. Zhang, C. Li, Y. Luo, Aligned/Unaligned conducting polymer cryogels with hydrogels for medical electrode applications, Sci. Technol. Adv. Mater. 11 (2010),
three dimensional macroporous architectures from ice segregation-Induced self- 014107.
assembly of PEDOT:PSS, Langmuir 27 (5) (2011) 1915–1923. [202] C. Kleber, M. Bruns, K. Lienkamp, J. Rühe, M. Asplund, An interpenetrating,
microstructurable and covalently attached conducting polymer hydrogel for
neural interfaces, Acta Biomater. 58 (2017) 365–375.
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Synthetic Metals 273 (2021) 116709

Contents lists available at ScienceDirect

PEDOT and PEDOT:PSS conducting polymeric hydrogels: A report on their

1. Introduction 1.1. Importance of CP’s

Table 2 1.3. Synthetic methods of CPH’s

Fig. 11. PEDOT:PSS hydrogel patterning using electrogelation method.

Fig. 14. (a) Experimental setup for stimulation

without compromising the conductivity of hydrogel. The in vitro cell

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