Bioinspired polypyrrole based fibrillary artificial muscle with actuation and intrinsic sensing capabilities.

A non-conventional, bioinspired device based on polypyrrole coated electrospun fibrous microstructures, which simultaneously works as artificial muscle and mechanical sensor is reported. Fibrous morphology is preferred due to its high active surface which can improve the actuation/sensing properties, its preparation still being challenging. Thus, a simple fabrication algorithm based on electrospinning, sputtering deposition and electrochemical polymerization produced electroactive aligned ribbon meshes with analogous characteristics as natural muscle fibers. These can simultaneously generate a movement (by applying an electric current/potential) and sense the effort of holding weights (by measuring the potential/current while holding objects up to 21.1 mg). Electroactivity was consisting in a fast bending/curling motion, depending on the fiber strip width. The amplitude of the movement decreases by increasing the load, a behavior similar with natural muscles. Moreover, when different weights were hung on the device, it senses the load modification, demonstrating a sensitivity of about 7 mV/mg for oxidation and - 4 mV/mg for reduction. These results are important since simultaneous actuation and sensitivity are essential for complex activity. Such devices with multiple functionalities can open new possibilities of applications as e.g. smart prosthesis or lifelike robots.

Enhancing the electrocatalytic activity and stability of Prussian blue analogues by increasing their electroactive sites through the introduction of Au nanoparticles.

Prussian blue analogues (PBAs) have been proven as excellent Earth-abundant electrocatalysts for the oxygen evolution reaction (OER) in acidic, neutral and alkaline media. Further improvements can be achieved by increasing their electrical conductivity, but scarce attention has been paid to quantify the electroactive sites of the electrocatalyst when this enhancement occurs. In this work, we have studied how the chemical design influences the specific density of electroactive sites in different Au-PBA nanostructures. Thus, we have first obtained and fully characterized a variety of monodisperse core@shell hybrid nanoparticles of Au@PBA (PBA of NiIIFeII and CoIIFeII) with different shell sizes. Their catalytic activity is evaluated by studying the OER, which is compared to pristine PBAs and other Au-PBA heterostructures. By using the coulovoltammetric technique, we have demonstrated that the introduction of 5-10% of Au in weight in the core@shell leads to an increase in the electroactive mass and thus, to a higher density of active sites capable of taking part in the OER. This increase leads to a significant decrease in the onset potential (up to 100 mV) and an increase (up to 420%) in the current density recorded at an overpotential of 350 mV. However, the Tafel slope remains unchanged, suggesting that Au reduces the limiting potential of the catalyst with no variation in the reaction kinetics. These improvements are not observed in other Au-PBA nanostructures mainly due to a lower contact between both compounds and the Au oxidation. Hence, an Au core activates the PBA shell and increases the conductivity of the resulting hybrid, while the PBA shell prevents Au oxidation. The strong synergistic effect existing in the core@shell structure evidences the importance of the chemical design for preparing PBA-based nanostructures exhibiting better electrocatalytic performances and higher electrochemical stabilities.

Multifunctionality of Polypyrrole Polyethyleneoxide Composites: Concurrent Sensing, Actuation and Energy Storage.

In films of conducting polymers, the electrochemical reaction(s) drive the simultaneous variation of different material properties (reaction multifunctionality). Here, we present a parallel study of actuation-sensing-energy storage triple functionality of polypyrrole (PPy) blends with dodecylbenzenesulfonate (DBS-), PPy/DBS, without and with inclusion of polyethyleneoxide, PPy-PEO/DBS. The characterization of the response of both materials in aqueous solutions of four different salts indicated that all of the actuating, sensing and charge storage responses were, independent of the electrolyte, present for both materials, but stronger for the PPy-PEO/DBS films: 1.4× higher strains, 1.3× higher specific charge densities, 2.5× higher specific capacitances and increased ion-sensitivity towards the studied counterions. For both materials, the reaction energy, the material potential and the strain variations adapt to and sense the electrical and chemical (exchanged cation) conditions. The driving and the response of actuation, sensing and charge can be controlled/read, simultaneously, via just two connecting wires. Only the cooperative actuation of chemical macromolecular motors from functional cells has such chemical multifunctionality.

Concept of an artificial muscle design on polypyrrole nanofiber scaffolds.

Here we present the synthesis and characterization of two new conducting materials having a high electro-chemo-mechanical activity for possible applications as artificial muscles or soft smart actuators in biomimetic structures. Glucose-gelatin nanofiber scaffolds (CFS) were coated with polypyrrole (PPy) first by chemical polymerization followed by electrochemical polymerization doped with dodecylbenzensulfonate (DBS-) forming CFS-PPy/DBS films, or with trifluoromethanesulfonate (CF3SO3-, TF) giving CFS-PPy/TF films. The composition, electronic and ionic conductivity of the materials were determined using different techniques. The electro-chemo-mechanical characterization of the films was carried out by cyclic voltammetry and square wave potential steps in bis(trifluoromethane)sulfonimide lithium solutions of propylene carbonate (LiTFSI-PC). Linear actuation of the CFS-PPy/DBS material exhibited 20% of strain variation with a stress of 0.14 MPa, rather similar to skeletal muscles. After 1000 cycles, the creeping effect was as low as 0,2% having a good long-term stability showing a strain variation per cycle of -1.8% (after 1000 cycles). Those material properties are excellent for future technological applications as artificial muscles, batteries, smart membranes, and so on.

Structural and Conformational Chemistry from Electrochemical Molecular Machines. Replicating Biological Functions. A Review.

Each constitutive chain of a conducting polymer electrode acts as a reversible multi-step electrochemical molecular motor: reversible reactions drive reversible conformational movements of the chain. The reaction-driven cooperative actuation of those molecular machines generates, or destroys, inside the film the free volume required to lodge/expel balancing counterions and solvent: reactions drive reversible film volume variations, which basic structural components are here identified and quantified from electrochemical responses. The content of the reactive dense gel (chemical molecular machines, ions and water) mimics that of the intracellular matrix in living functional cells. Reaction-driven properties (composition-dependent properties) and devices replicate biological functions and organs. An emerging technological world of soft, wet, reaction-driven, multifunctional and biomimetic devices and the concomitant zoomorphic or anthropomorphic robots is presented.

Electrospun silk fibroin scaffolds coated with reduced graphene promote neurite outgrowth of PC-12 cells under electrical stimulation.

Novel approaches to neural research require biocompatible materials capable to act as electrode structures or scaffolds for tissue engineering in order to stimulate or restore the functionality of damaged tissues. This work offers promising results that indicate the potential use of electrospun silk fibroin (SF) scaffolds coated with reduced graphene oxide (rGO) in this sense. The coated material becomes conductor and electroactive. A complete characterisation of SF/rGO scaffolds is provided in terms of electrochemistry, mechanical behaviour and chemical conformation of fibroin. The excellent biocompatibility of this novel material is proved with cultures of PC-12 cells. The coating with rGO improved the adhesion of cells in comparison with cells growing onto the surface of pure SF scaffolds. Also, the use of SF/rGO scaffolds combined with electrical stimulation promoted the differentiation into neural phenotypes reaching comparable or even superior levels to those obtained by means of the traditional treatment with neural growth factor (NGF).

Self-Supported Polypyrrole/Polyvinylsulfate Films: Electrochemical Synthesis, Characterization, and Sensing Properties of Their Redox Reactions.

Invited for this month's cover picture is the group of Professor Toribio F. Otero at the Centre for Electrochemistry, Intelligent Materials and Devices at the Polytechnic University of Cartagena (Spain). The cover picture shows an electrochemical cell as well as three representative cyclic voltammetric responses, displaying the electrolyte potential window, the monomer oxidation-polymerization potential range, and the polymer oxidation-reduction potential window. For more details, read the full text of the Full Paper at 10.1002/open.201600139.

Self-Supported Polypyrrole/Polyvinylsulfate Films: Electrochemical Synthesis, Characterization, and Sensing Properties of Their Redox Reactions.

Thick films of polypyrrole/polyvinylsulfate (PPy/PVS) blends were electrogenerated on stainless-steel electrodes under potentiostatic conditions from aqueous solution. The best electropolymerization potential window was determined by cyclic voltammetry. After removing the film from the back metal, self-supported electrodes were obtained. Voltammetric, coulovoltammetric, and chronoamperometric responses from a LiClO4 aqueous solution indicated the formation of an energetically stable structure beyond a reduction threshold of the material. Its subsequent oxidation required higher anodic voltammetric overpotentials or longer chronoamperometric oxidation times. This structure was attributed to the formation of lamellar or vacuolar structures. X-ray photoelectron spectroscopy analysis of the films under different oxidations states revealed that the electrochemical reactions drive the reversible exchange of cations between the film and the electrolyte. The electrical energy and the charge consumed by the reversible reaction of the film under voltammetric conditions between the constant potential limits are a function of the potential scan rate, that is, they sense the working electrochemical conditions.

Reactions driving conformational movements (molecular motors) in gels: conformational and structural chemical kinetics.

In this perspective the empirical kinetics of conducting polymers exchanging anions and solvent during electrochemical reactions to get dense reactive gels is reviewed. The reaction drives conformational movements of the chains (molecular motors), exchange of ions and solvent with the electrolyte and structural (relaxation, swelling, shrinking and compaction) gel changes. Reaction-driven structural changes are identified and quantified from electrochemical responses. The empirical reaction activation energy (Ea), the reaction coefficient (k) and the reaction orders (α and ß) change as a function of the conformational energy variation during the reaction. This conformational energy becomes an empirical magnitude. Ea, k, α and ß include and provide quantitative conformational and structural information. The chemical kinetics becomes structural chemical kinetics (SCK) for reactions driving conformational movements of the reactants. The electrochemically stimulated conformational relaxation model describes empirical results and some results from the literature for biochemical reactions. In parallel the development of an emerging technological world of soft, wet, multifunctional and biomimetic tools and anthropomorphic robots driven by reactions of the constitutive material, as in biological organs, can be now envisaged being theoretically supported by the kinetic model.

Fabrication of electrospun silk fibroin scaffolds coated with graphene oxide and reduced graphene for applications in biomedicine.

Silk fibroin and graphene are both promising biomaterials described in the bibliography. Hybrid scaffolds combining their properties could be attractive for tissue engineering applications. In this work, a new methodology to produce electrospun fibroin scaffolds coated with graphene materials is provided. The mechanical, electrical and electrochemical properties of the materials attained were characterised. The fibre diameters were measured (from 3.9 to 5.2 µm). The samples coated with reduced grapheme were electronic conductors and electroactive in liquid electrolytes, showing maximum oxidation and reduction (around−0.4 V peak). The chronoamperometric responses showed a reduction shoulder, pointing to the entrance of balancing cations from the solution by nucleation­relaxation: the reaction induced structural changes in the graphene. In order to check the biocompatibility of the materials, they were seeded with L929 fibroblasts. The excellent biocompatibility of silk fibroin meshes was maintained after coating with graphene, being the proliferation results equal in all the treatments 7 days after the seeding (Tukey, p N 0.05).The conductive and electroactive properties of meshes coated with reduced graphene allow the potential application of local electric fields or local ionic currents to cell cultures, biological interfaces or animal models without host response.

Deep Reduced PEDOT Films Support Electrochemical Applications: Biomimetic Color Front.

Most of the literature accepts, despite many controversial results, that during oxidation/reduction films of conducting polymers (CPs) move from electronic conductors to insulators. Thus, engineers and device's designers are forced to use metallic supports to reoxidize the material for reversible device work. Electrochromic front experiments appear as main visual support of the claimed insulating nature of reduced CPs. Here, we present a different design of the biomimetic electrochromic front that corroborates the electronic and ionic conducting nature of deep reduced films. The direct contact PEDOT metal/electrolyte and film/electrolyte was prevented from electrolyte contact until 1 cm far from the metal contact with protecting Parafilm(®). The deep reduced PEDOT film supports the flow of high currents promoting reaction induced electrochromic color changes beginning 1 cm far from the metal-polymer electrical contact and advancing, through the reduced film, toward the metal contact. Reverse color changes during oxidation/reduction always are initiated at the film/electrolyte contact advancing, under the protecting film, toward the film/metal contact. Both reduced and oxidized states of the film demonstrate electronic and ionic conductivities high enough to be used for electronic applications or, as self-supported electrodes, for electrochemical devices. The electrochemically stimulated conformational relaxation model explains those results.

Effect of the electrolyte concentration and substrate on conducting polymer actuators.

The effect of the electrolyte concentration (NaCl aqueous electrolyte) on the dimensional variations of films of polypyrrole doped with dodecylbenzenesulfonate PPy(DBS) on Pt and Au wires was studied. Any parallel reaction that occurs during the redox polymeric reaction that drives the mechanical actuation, as detected from the coulovoltammetric responses, was avoided by using Pt wires as substrate and controlling the potential limits, thus significantly increasing the actuator lifetime. The NaCl concentration of the electrolyte, when studied by cyclic voltammetry or chronoamperometry, has a strong effect on the performance as well. A maximum expansion was achieved in 0.3 M aqueous solution. The consumed oxidation and reduction charges control the fully reversible dimensional variations: PPy(DBS) films are faradaic polymeric motors. Parallel to the faradaic exchange of the cations, osmotic, electrophoretic, and structural changes play an important role for the water exchange and volume change of PPy(DBS).

Exchanged cations and water during reactions in polypyrrole macroions from artificial muscles.

The movement of the bilayer (polypyrrole-dodecylbenzenesulfonate/tape) during artificial muscle bending under flow of current square waves was studied in aqueous solutions of chloride salts. During current flow, polypyrrole redox reactions result in variations in the volumes of the films and macroscopic bending: swelling by reduction with expulsion of cations and shrinking by oxidation with the insertion of cations. The described angles follow a linear function, different in each of the studied salts, of the consumed charge: they are faradaic polymeric muscles. The linearity indicates that cations are the only exchanged ions in the studied potential range. By flow of the same specific charge in every electrolyte, different angles were described by the muscle. The charge and the angle allow the number and volume of both the exchanged cations and the water molecules (related to a reference) between the film to be determined, in addition to the electrolyte per unit of charge during the driving reaction. The attained apparent solvation numbers for the exchanged cations were: 0.8, 0.7, 0.6, 0.5, 0.5, 0.4, 0.25, and 0.0 for Na(+), Mg(2+), La(3+), Li(+), Ca(2+), K(+), Rb(+), and Cs(+), respectively.

Polypyrrole-para-phenolsulfonic acid/tape artificial muscle as a tool to clarify biomimetic driven reactions and ionic exchanges.

Thick films of the polypyrrole-para-phenolsulfonic acid (PPy-HpPS) blend were electrogenerated on stainless steel plates. The self-supported films, once peeled off from the metal, were electrochemically characterized in aqueous solutions of NaCl and NaPF6. The Na, Cl, P, S and F content of films, after attaining a different oxidation state, were determined by EDX. The bending movements of the bilayer (PPy-HpPS)/tape artificial muscle were video recorded during potential sweeps in both solutions allowing the translation of the prevalent ionic exchanges driven by the biomimetic reactions into macroscopic movements. Ionic exchanges between the film and the solution, biomimetic structural processes in the film, driving prevalent electrochemical reactions and film compositions related to each of the different structural potential domains defined by coulovoltammetric results were clarified. In NaPF6 solutions a prevalent exchange of anions exists: the film swells by oxidation and shrinks by reduction. In NaCl solutions prevailing exchange of cations or anions occurs in different potential ranges. Reactions related to the HpPS content play important roles at the more cathodic and more anodic overpotentials. The described methodology could be translated to biological reactions including reactive biopolymers.

Biomimetic intracellular matrix (ICM) materials, properties and functions. Full integration of actuators and sensors.

The electrochemistry of conducting polymers, and other organic compounds, originates biomimetic (intracellular matrix, ICM, reactive gels) materials, properties and devices here reviewed. One reaction changes several properties (multifunctionality): one device can integrate different actuators (artificial muscles, batteries, smart windows) and sensors (temperature, concentration, mechanical). Actuating (current and charge) and sensing (potential) magnitudes are present in the two connecting wires, and can be read by the computer, at any working time mimicking brain-organs dialog. The theoretical description of any multi-functional device envisages intelligent gel robots. The kinetic magnitudes of the reaction become a function of the conformational structure: predictive structural, chemical and biochemical kinetics are emerging.

Reactions drive conformations. Biomimetic properties and devices, theoretical description.

Life is supported by cellular reactions driving conformational, folding and unfolding macromolecular movements with ionic and aqueous exchange. Here we review the state of the art of the electrochemistry of conducting polymers as elemental material models of biological reactive gels. The different experimental methodologies allowing identification and quantification of the reaction induced molecular (conformation) and macroscopic (relaxation, swelling, shrinking and compaction) structural changes are reviewed. Similar structural effects from other materials and systems, artificial or biological, are presented. Some reaction induced properties and devices mimicking biological functions and organs are described: sensing and tactile artificial muscles, smart membranes, artificial glands or artificial chemical synapses. The new structural chemical kinetics opens the way to modelling and predicting health issues linked to reactive folding or misfolding processes, and to advancing the knowledge of brain molecular mechanisms such as memory. Chemo-electronic conformational memories and dual sensing-actuating, zoomorphic and anthropomorphic gel tools and robots are envisaged.

Biomimetic dual sensing-actuators: theoretical description. Sensing electrolyte concentration and driving current.

Here we present the theoretical (electrochemical and polymeric) description of chronopotentiometric responses (under driven constant current) from reacting conducting polymers both, as films or taking part of electrochemical devices, that sense driving current and electrolyte concentration during reactive actuation. The attained sensing-actuation equations describe the potential, or the consumed electrical energy, evolution as a function of working and environmental variables: driving current, temperature, electrolyte concentration, or mechanical conditions. Good agreement between theoretical and experimental results is attained here by using polypyrrole films under flow of different currents or in different electrolyte concentrations. Being a general theoretical description, any reactive device based on the electrochemistry of conducting polymers or carbon based reactive compounds is expected to sense working and environmental conditions being described by those equations as tactile artificial muscles do. Only two connecting wires contain actuating (current) and sensing (potential) signals that are detected, simultaneously and at any actuating time, by the computer as mammalians brains do.

Electrochemistry of carbon nanotubes: reactive processes, dual sensing-actuating properties and devices.

Single-walled carbon nanotubes (SWCNT) embedded in a non-electroactive polymer are electrochemically characterized. The increasing voltammetric maximums obtained with rising temperature or electrolyte concentration point to a chemical nature of the processes. The chemical kinetic control of the processes is corroborated by its empirical chemical kinetics: the initial reaction rates are obtained from the chronoamperometric responses to potential steps. The activation energy of the reaction includes information about the structural state of the SWCNT before the potential step. Under constant current the potential evolution (chronopotentiometric response) and consumed electrical energy at any time change as a function of (are sensors of) the experimental temperature or the electrolyte concentration. The reactive material, or any device based on this material, senses these working variables, and shows dual and simultaneous actuating-sensing properties.

Biomimetic dual sensing-actuators based on conducting polymers. Galvanostatic theoretical model for actuators sensing temperature.

A theoretical model is proposed for the quantitative description of the chronopotentiometric (E-t) responses, under galvanostatic control, of either conducting polymer films or dual sensing-actuating devices. Assuming that the reaction occurs by extraction, or injection, of n consecutive electrons from, or to, a polymer chain the material moves through n consecutive oxidation or reduction states. Stair functions are obtained describing either potential or consumed electrical energy evolutions as a function of both, driving (current) and environmental (temperature, electrolyte concentration...) variables. The current quantifies the actuation of any electrochemical device (charge/discharge of batteries, movement rate, and position of muscles): the stair functions are dual actuating-sensing functions. A good agreement exists between theoretical and experimental results from either polypyrrole films or artificial muscles at different temperatures. Only two connecting wires include, at any time, sensing (potential) and working (current) information of any dual device.

Fabrication of conductive electrospun silk fibroin scaffolds by coating with polypyrrole for biomedical applications.

Scaffolds constituted by micro and nanofibers of silk fibroin were obtained by electrospinning. Fibers of fibroin meshes were coated with polypyrrole (pPy) by chemical polymerization; chemical linkages between polymers were observed by SEM and IR spectroscopy. Mechanical resistance of the meshes was improved by polypyrrole coating. Furthermore, coated meshes present a high electroactivity allowing anion storage and delivery during oxidation/reduction reactions in aqueous solutions. Uncoated and pPy coated materials support the adherence and proliferation of adult human mesenchymal stem cells (ahMSCs) or human fibroblasts (hFb). The bioactivity of fibroin mesh overcomes that of the polypyrrole coated meshes.