Electroactive 4D Porous Scaffold Based on Conducting Polymer as a Responsive and Dynamic In Vitro Cell Culture Platform.

In vivo, cells reside in a 3D porous and dynamic microenvironment. It provides biochemical and biophysical cues that regulate cell behavior in physiological and pathological processes. In the context of fundamental cell biology research, tissue engineering, and cell-based drug screening systems, a challenge is to develop relevant in vitro models that could integrate the dynamic properties of the cell microenvironment. Taking advantage of the promising high internal phase emulsion templating, we here designed a polyHIPE scaffold with a wide interconnected porosity and functionalized its internal 3D surface with a thin layer of electroactive conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) to turn it into a 4D electroresponsive scaffold. The resulting scaffold was cytocompatible with fibroblasts, supported cellular infiltration, and hosted cells, which display a 3D spreading morphology. It demonstrated robust actuation in ion- and protein-rich complex culture media, and its electroresponsiveness was not altered by fibroblast colonization. Thanks to customized electrochemical stimulation setups, the electromechanical response of the polyHIPE/PEDOT scaffolds was characterized in situ under a confocal microscope and showed 10% reversible volume variations. Finally, the setups were used to monitor in real time and in situ fibroblasts cultured into the polyHIPE/PEDOT scaffold during several cycles of electromechanical stimuli. Thus, we demonstrated the proof of concept of this tunable scaffold as a tool for future 4D cell culture and mechanobiology studies.

Electroactive Bi-Functional Liquid Crystal Elastomer Actuators.

Liquid crystal elastomers (LCEs) with promising applications in the field of actuators and soft robotics are reported. However, most of them are activated by external heating or light illumination. The examples of electroactive LCEs are still limited; moreover, they are monofunctional with one type of deformation (bending or contraction). Here, the study reports on trilayer electroactive LCE (eLCE) by intimate combination of LCE and ionic electroactive polymer device (i-EAD). This eLCE is bi-functional and can perform either bending or contractile deformations by the control of the low-voltage stimulation. By applying a voltage of ±2 V at 0.1 Hz, the redox behavior and associated ionic motion provide a bending strain difference of 0.80%. Besides, by applying a voltage of ±6 V at 10 Hz, the ionic current-induced Joule heating triggers the muscle-like linear contraction with 20% strain for eLCE without load. With load, eLCE can lift a weight of 270 times of eLCE-actuator weight, while keeping 20% strain and affording 5.38 kJ·m-3 work capacity. This approach of combining two smart polymer technologies (LCE and i-EAD) in a single device is promising for the development of smart materials with multiple degrees of freedom in soft robotics, electronic devices, and sensors.

Intrinsically Stretchable Integrated Passive Matrix Electrochromic Display Using PEDOT:PSS Ionic Liquid Composite.

The low power consumption of electrochromism makes it widely used in actively shaded windows and mirrors, while flexible versions are attractive for use in wearable devices. Initial demonstration of stretchable electrochromic elements promises good conformability to complex surfaces. Here, fully integrated intrinsically stretchable electrochromic devices are demonstrated as single elements and 3 × 3 displays. Conductive and electrochromic ionic liquid-doped poly(3,4-ethylenedioxythiophene) polystyrene sulfonate is combined with poly(vinyl alcohol)-based electrolyte to form complete cells. A transmission change of 15% is demonstrated, along with a reflectance change of 25% for opaque reflective devices, with <7 s switching time, even under 30% strain. Stability under both electrochemical and mechanical strain cycling is demonstrated. A passive matrix display exhibits addressability and low cross-talk under strain. Comparable optical performance to flexible electrochromics and higher deformability provide attractive qualities for use in wearable, biometric monitoring, and robotic skin devices.

Vitrimer ionogels towards sustainable solid-state electrolytes.

The growing demand for flexible, stretchable, and wearable devices has boosted the development of ionogels used as polymer electrolytes. Developing healable ionogels based on vitrimer chemistry is a promising approach to improve their lifetimes as these materials are usually subjected to repeated deformation during functioning and are susceptible to damage. In this work, we reported in the first place the preparation of polythioether vitrimer networks based on the not extensively studied associative S-transalkylation exchange reaction using thiol-ene Michael addition. Thanks to the exchange reaction of sulfonium salts with thioether nucleophiles, these materials demonstrated vitrimer properties such as healing and stress relaxation. The fabrication of dynamic polythioether ionogels was then demonstrated by loading 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIM triflate) within the polymer network. The resulting ionogels exhibited Young's modulus of 0.9 MPa and ionic conductivities in the order of 10-4 S cm-1 at room temperature. It has been found that adding ionic liquids (ILs) changes the dynamic properties of the systems, most likely due to a dilution effect of the dynamic functions by the IL but also due to a screening effect of the alkyl sulfonium OBrs-couple by the ions of the IL itself. To the best of our knowledge, these are the first vitrimer ionogels based on an S-transalkylation exchange reaction. While the addition of ILs resulted in less efficient dynamic healing at a given temperature, these ionogels can provide materials with more dimensional stability at application temperatures and can potentially pave the way for the development of tunable dynamic ionogels for flexible electronics with a longer lifespan.

Healable Ionoelastomer Designed from Polymeric Ionic Liquid and Vitrimer Chemistry.

The growing demand for all-solid flexible, stretchable, and wearable devices has boosted the need for liquid-free and stretchable ionoelastomers. These ionic conducting materials are subjected to repeated deformations during functioning, making them susceptible to damage. Thus, imparting cross-linked materials with healing ability seems particularly promising to improve their durability. Here, a polymeric ionic liquid (PIL) bearing allyl functional groups was synthesized based on the quaternization of N-allylimidazole with a copolymer rubber of poly(epichlorohydrin) and poly(ethylene oxide) (PEO). The resulting PIL was then cross-linked with dynamic boronic ester cross-linkers 2,2'-(1,4-Phenylene)-bis[4-mercaptan-1,3,2-dioxaborolane] (BDB) through thiol-ene "click" photoaddition. PEO dangling chains were additionally introduced for acting as free volume enhancers. The properties of the resulting all-solid PIL networks were investigated by tuning dynamic cross-linkers and dangling chain contents. Adjusting the cross-linker and dangling chain quantities yielded soft (0.2 MPa), stretchable (300%), and highly conducting ionoelastomers (1.6 × 10-5 S·cm-1 at 30 °C). The associative exchange reaction between BDB endowed these materials with vitrimer properties such as healing and recyclability. The recycled materials were able to retain their original mechanical properties and ionic conductivity. These healable PIL networks display a great potential for applications requiring solid electrolytes with high ionic conductivity, healing ability, and reprocessability.

Photopolymerizable Ionogel with Healable Properties Based on Dioxaborolane Vitrimer Chemistry.

Ionogels are solid polymer gel networks loaded with ionic liquid (IL) percolating throughout each other, giving rise to ionically conducting solid electrolytes. They combine the mechanical properties of polymer networks with the ionic conductivity, non-volatility, and non-flammability of ILs. In the frame of their applications in electrochemical-based flexible electronics, ionogels are usually subjected to repeated deformation, making them susceptible to damage. It appears critical to devise a simple and effective strategy to improve their durability and lifespan by imparting them with healing ability through vitrimer chemistry. In this work, we report the original in situ synthesis of polythioether (PTE)-based vitrimer ionogels using fast photopolymerization through thiol-acrylate Michael addition. PTE-based vitrimer was prepared with a constant amount of the trithiol crosslinker and varied proportions of static dithiol spacers and dynamic chain extender BDB containing dynamic exchangeable boronic ester groups. The dynamic ionogels were prepared using 50 wt% of either 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide or 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate, both of which were selected for their high ionic conductivity. They are completely amorphous (Tg below -30 °C), suggesting they can be used at low temperatures. They are stretchable with an elongation at break around 60%, soft with Young's modulus between 0.4 and 0.6 MPa, and they have high ionic conductivities for solid state electrolytes in the order of 10-4 S·cm-1 at room temperature. They display dynamic properties typical of the vitrimer network, such as stress relaxation and healing, retained despite the large quantity of IL. The design concept illustrated in this work further enlarges the library of vitrimer ionogels and could potentially open a new path for the development of more sustainable, flexible electrochemical-based electronics with extended service life through repair or reprocessing.

Piezoionic mechanoreceptors: Force-induced current generation in hydrogels.

The human somatosensory network relies on ionic currents to sense, transmit, and process tactile information. We investigate hydrogels that similarly transduce pressure into ionic currents, forming a piezoionic skin. As in rapid- and slow-adapting mechanoreceptors, piezoionic currents can vary widely in duration, from milliseconds to hundreds of seconds. These currents are shown to elicit direct neuromodulation and muscle excitation, suggesting a path toward bionic sensory interfaces. The signal magnitude and duration depend on cationic and anionic mobility differences. Patterned hydrogel films with gradients of fixed charge provide voltage offsets akin to cell potentials. The combined effects enable the creation of self-powered and ultrasoft piezoionic mechanoreceptors that generate a charge density four to six orders of magnitude higher than those of triboelectric and piezoelectric devices.

Evaluation of dielectric elastomers to develop materials suitable for actuation.

Electroactive polymers based on dielectric elastomers are stretchable and compressible capacitors that can act as transducers between electrical and mechanical energies. Depending on the targeted application, soft actuators, sensors or mechanical-energy harvesters can be developed. Compared with conventional technologies, they present a promising combination of properties such as being soft, silent, light and miniaturizable. Most of the research on dielectric elastomer actuators has focused on obtaining the highest strain, either from technological solutions using commercially available materials or through the development of new materials. It is commonly accepted that a high electrical breakdown field, a low Young's modulus and a high dielectric constant are targets. However, the interdependency of these properties makes the evaluation and comparison of these materials complex. In addition, dielectric elastomers can suffer from electromechanical instability, which amplifies their complexity. The scope of this review is to tackle these difficulties. Thus, first, two physical parameters are introduced, one related to the energy converted by the dielectric elastomer and another to its electromechanical stability. These numbers are then used to compare dielectric elastomers according to a general and rational methodology considering their physicochemical and electromechanical properties. Based on this methodology, different families of commercially available dielectric elastomers are first analyzed. Then, different polymer modification methods are presented, and the resulting modified elastomers are screened. Finally, we conclude on the trends enabling the choice of the most suitable modification procedure to obtain the desired elastomer. From this review work, we would like to contribute to affording a quick identification method, including a graphic representation, to evaluate and develop the dielectric materials that are suitable for a desired actuator.

Pushing the Limits of Flexibility and Stretchability of Solar Cells: A Review.

Emerging forms of soft, flexible, and stretchable electronics promise to revolutionize the electronics industries of the future offering radically new products that combine multiple functionalities, including power generation, with arbitrary form factor. For example, skin-like electronics promise to transform the human-machine-interface, but the softness of the skin is incompatible with traditional electronic components. To address this issue, new strategies toward soft and wearable electronic systems are currently being pursued, which also include stretchable photovoltaics as self-powering systems for use in autonomous and stretchable electronics of the future. Here recent developments in the field of stretchable photovoltaics are reviewed and their potential for various emerging applications are examined. Emphasis is placed on the different strategies to induce stretchability including extrinsic and intrinsic approaches. In the former case, engineering and patterning of the materials and devices are key elements while intrinsically stretchable systems rely on mechanically compliant materials such as elastomers and organic conjugated polymers. The result is a review article that provides a comprehensive summary of the progress to date in the field of stretchable solar cells from the nanoscale to macroscopic functional devices. The article is concluded by discussing the emerging trends and future developments.

Printed PEDOT:PSS Trilayer: Mechanism Evaluation and Application in Energy Storage.

Combining ink-jet printing and one of the most stable electroactive materials, PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)), is envisaged to pave the way for the mass production of soft electroactive materials. Despite its being a well-known electroactive material, widespread application of PEDOT:PSS also requires good understanding of its response. However, agreement on the interpretation of the material's activities, notably regarding actuation, is not unanimous. Our goal in this work is to study the behavior of trilayers with PEDOT:PSS electrodes printed on either side of a semi-interpenetrated polymer network membrane in propylene carbonate solutions of three different electrolytes, and to compare their electroactive, actuation, and energy storage behavior. The balance of apparent faradaic and non-faradaic processes in each case is discussed. The results show that the primarily cation-dominated response of the trilayers in the three electrolytes is actually remarkably different, with some rather uncommon outcomes. The different balance of the apparent charging mechanisms makes it possible to clearly select one electrolyte for potential actuation and another for energy storage application scenarios.

Conducting and Stretchable PEDOT:PSS Electrodes: Role of Additives on Self-Assembly, Morphology, and Transport.

The addition of dimethylsulfoxide and Zonyl into poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) can be combined to achieve excellent electrical, optical, and mechanical properties. We demonstrate that it is possible to produce highly transparent conducting electrodes (FoM > 35) with low Young's modulus and high carrier density. We investigated the relationship between the transport properties of PEDOT:PSS and the morphology and microstructure of these films by performing Hall effect measurement, atomic force microscopy, and grazing incidence wide-angle X-ray scattering (GIWAXS). Our analysis reveals the distinctive impact of the two additives on the PEDOT and PSS components in the solid-state PEDOT:PSS films. Both additives induce fibrillar formation in the film, and the combination of the two additives only enhances the fibrillary nature and the aggregations of both PEDOT and PSS components of the film. In situ GIWAXS allows to time-resolve the morphology evolution. Our analysis reveals the influence of additives on the aggregation and self-assembly behaviors of the PEDOT and PSS components. Aggregation occurs during the transition from wet to dry film, which is observed exclusively during the thermal annealing step of the as-cast hydrated film. These results indicate that the additives directly influence the self-assembly behaviors of PEDOT and PSS during the ink-to-solid phase transformation of the hydrated film, which occurs primarily during the initial seconds of post-deposition thermal annealing.

Highly Conductive, Photolithographically Patternable Ionogels for Flexible and Stretchable Electrochemical Devices.

An ionic conducting membrane is an essential part in various electrochemical devices including ionic actuators. To miniaturize these devices, micropatterns of ionic conducting membrane are desired. Here, we present a novel type of ionogel that can be patterned using standard photolithography and soft imprinting lithography. The ionogel is prepared in situ by UV-initiated free-radical polymerization of thiol acrylate precursors in the presence of ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. The resultant ionogel is very flexible with a low Young's modulus (as low as 0.23 MPa) and shows a very high ionic conductivity (up to 2.4 × 10-3 S/cm with 75 wt % ionic liquid incorporated) and has a reactive surface due to the excess thiol groups. Micropatterns of ionogel are obtained by using the thiol acrylate ionogel solution as an ionic conducting photoresist with standard photolithography. Water, a solvent immiscible with ionic liquid, is used as the photoresist developer to avoid complete removal of ionic liquid from thin micropatterns of the ionogel. By taking advantage of the reactive surface of ionogels and the photopatternability, ionogels with complex three-dimensional microstructure are developed. The surface of the ionogels can also be easily patterned using UV-assisted soft imprinting lithography. This new type of ionogels may open up for building high-performance flexible electrochemical microdevices.

Conducting electrospun fibres with polyanionic grafts as highly selective, label-free, electrochemical biosensor with a low detection limit for non-Hodgkin lymphoma gene.

A highly selective, label-free sensor for the non-Hodgkin lymphoma gene, with an aM detection limit, utilizing electrochemical impedance spectroscopy (EIS) is presented. The sensor consists of a conducting electrospun fibre mat, surface-grafted with poly(acrylic acid) (PAA) brushes and a conducting polymer sensing element with covalently attached oligonucleotide probes. The sensor was fabricated from electrospun NBR rubber, embedded with poly(3,4-ethylenedioxythiophene) (PEDOT), followed by grafting poly(acrylic acid) brushes and then electrochemically polymerizing a conducting polymer monomer with ssDNA probe sequence pre-attached. The resulting non-Hodgkin lymphoma gene sensor showed a detection limit of 1aM (1 × 10-18mol/L), more than 400 folds lower compared to a thin-film analogue. The sensor presented extraordinary selectivity, with only 1%, 2.7% and 4.6% of the signal recorded for the fully non-complimentary, T-A and G-C base mismatch oligonucleotide sequences, respectively. We suggest that such greatly enhanced selectivity is due to the presence of negatively charged carboxylic acid moieties from PAA grafts that electrostatically repel the non-complementary and mismatch DNA sequences, overcoming the non-specific binding.

Top-down Approach for the Direct Synthesis, Patterning, and Operation of Artificial Micromuscles on Flexible Substrates.

Recent progress in the field of microsystems on flexible substrates raises the need for alternatives to the stiffness of classical actuation technologies. This paper reports a top-down process to microfabricate soft conducting polymer actuators on substrates on which they ultimately operate. The bending microactuators were fabricated by sequentially stacking layers using a layer polymerization by layer polymerization of conducting polymer electrodes and a solid polymer electrolyte. Standalone microbeams thinner than 10 µm were fabricated on SU-8 substrates associated with a bottom gold electrical contact. The operation of microactuators was demonstrated in air and at low voltage (±4 V).

Graphitic carbon nitride nanosheet electrode-based high-performance ionic actuator.

Ionic actuators have attracted attention due to their remarkably large strain under low-voltage stimulation. Because actuation performance is mainly dominated by the electrochemical and electromechanical processes of the electrode layer, the electrode material and structure are crucial. Here, we report a graphitic carbon nitride nanosheet electrode-based ionic actuator that displays high electrochemical activity and electromechanical conversion abilities, including large specific capacitance (259.4 F g(-1)) with ionic liquid as the electrolyte, fast actuation response (0.5±0.03% in 300 ms), large electromechanical strain (0.93±0.03%) and high actuation stability (100,000 cycles) under 3 V. The key to the high performance lies in the hierarchical pore structure with dominant size <2 nm, optimal pyridinic nitrogen active sites (6.78%) and effective conductivity (382 S m(-1)) of the electrode. Our study represents an important step towards artificial muscle technology in which heteroatom modulation in electrodes plays an important role in promoting electrochemical actuation performance.

Smarter Actuator Design with Complementary and Synergetic Functions.

A general synthetic strategy for multifunctional actuators is presented, by confining desired functions in separate domains of interpenetrating polymer network materials. Specifically, complementary ionic actuator and shape-memory functions are demonstrated by simultaneous, orthogonal reaction pathways. Synergistic effects also allow dynamic programming and two-way linear shape-memory actuation.

Electrospun rubber fibre mats with electrochemically controllable pore sizes.

Electroactive, elastomeric, microfiber mats that show controllable pore size variation upon electrochemical stimulation are produced from semi-interpenetrating polymer networks (s-IPNs). This type of porous, elastomeric scaffolds that are mechanically dynamic under electrochemical stimuli could find new applications in stretchable electronics, (bio)filtration, soft robotics and stimulation of biological cells. These microfiber mats are prepared in two simple steps. Firstly, a mixture of high molecular weight nitrile butadiene rubber (NBR) and cross-linking agent, poly(ethylene glycol)dimethylacrylate are electrospun with in situ cross-linking. Secondly, a conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) is embedded into the electrospun fibres by oxidative chemical polymerization of EDOT-swollen microfiber mats. This two-step process affords robust, highly flexible and conductive s-IPN microfiber mats. The microfiber mat undergoes a controllable pore size variation upon applying an electrochemical stimulus in the form of a reduction-oxidation cycle to the mats in an electrolyte. The maximum average pore size variation, measured in situ using confocal microscopy, is 25%, achieved in 1 M lithium bis-trifluoromethanesulfonimide (LiTFSI) in propylene carbonate (PC) for a potential step between +0.6 V and -0.5 V (vs. Ag wire). These mats also show pore size variation in a biologically compatible solution, phosphate buffered saline.

Ionic electroactive polymer artificial muscles in space applications.

A large-scale effort was carried out to test the performance of seven types of ionic electroactive polymer (IEAP) actuators in space-hazardous environmental factors in laboratory conditions. The results substantiate that the IEAP materials are tolerant to long-term freezing and vacuum environments as well as ionizing Gamma-, X-ray, and UV radiation at the levels corresponding to low Earth orbit (LEO) conditions. The main aim of this material behaviour investigation is to understand and predict device service time for prolonged exposure to space environment.

A first truly all-solid state organic electrochromic device based on polymeric ionic liquids.

Using polymeric ionic liquids and PEDOT as ion conducting separators and electrodes, respectively, an all-polymer-based organic electrochromic device (ECD) has been constructed. The advantages of such an ECD are: fast switching time (3 s), high coloration efficiency (390 cm(2) C(-1) at 620 nm), optical contrast up to ΔT = 22% and the possibility of working under vacuum.

Conducting polymer artificial muscle fibres: toward an open air linear actuation.

We describe here a truly "one piece" electronic conducting polymer based linear actuator operating in the open air.