A PEDOT based graft copolymer with enhanced electronic stability.

Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) remains the most investigated conjugated polymer in bioelectronics, due to its biocompatibility, high conductivity, and commercial availability. Despite these advantages, it suffers from structural and electronic instability, associated with the PSS component. Here, a graft copolymer based on ionised sulfonic modified PEDOT, poly(EDOTS-g-EDOT), was electrochemically synthesised with demonstrated structural and electronic stability and enhanced electrochemical performance. The graft copolymer was insoluble in water without crosslinking, and exhibited enhanced ion diffusion upon electrochemical switching, as revealed by its volumetric capacitance (159 ± 8 F cm-3), which was significantly higher than that of spin-coated PEDOT:PSS films (41 ± 5 F cm-3). Similarly, its performance as an active channel material in organic electrochemical transistors (OECTs) was superior to the spin-coated PEDOT:PSS, as shown for instance by its high normalised transconductance (273 ± 79 S cm-1) and a significantly high ION/IOFF ratio (19 345 ± 1205). Its short- and long-term electronic stability were also confirmed with no drop in its output drain current, despite its high swelling degree. In contrast, the spin-coated PEDOT:PSS experienced a significant deterioration in its performance over the same operational time. The facile synthesis and improved performance of poly(EDOTS-g-EDOT) highlight the importance of innovative material design in overcoming existing operational shortcomings in electronic devices.

A Novel Cryogenic Approach to 3D Printing Cytocompatible, Conductive, Hydrogel-Based Inks.

In the field of tissue engineering and regenerative medicine, developing cytocompatible 3D conductive scaffolds that mimic the native extracellular matrix is crucial for the engineering of excitable cells and tissues. In this study, a custom cryogenic extrusion 3D printer was developed, which afforded control over both the ink and printing surface temperatures. Using this approach, aqueous inks were printed into well-defined layers with high precision. A conductive hydrogel ink was developed from chitosan (CS) and edge-functionalised expanded graphene (EFXG). Different EFXG:CS ratios (between 60:40 and 80:20) were evaluated to determine both conductivity and printability. Using the novel customized cryogenic 3D printer, conductive structures of between 2 and 20 layers were produced, with feature sizes as small as 200 µm. The printed structures are mechanically robust and are electrically conducting. The highest Young's modulus and conductivity in a hydrated state were 2.6 MPa and ∼45 S/m, respectively. Cytocompatibility experiments reveal that the developed material supports NSC-34 mouse motor neuron-like cells in terms of viability, attachment, and proliferation. The distinctive mechanical and electrical properties of the 3D-printed structures would make them good candidates for the engineering of 3D-structured excitable cells. Moreover, this novel printing setup can be used to print other hydrogel-based inks with high precision and resolution.

Edge-Functionalized Graphene/Polydimethylsiloxane Composite Films for Flexible Neural Cuff Electrodes.

The design of neural electrodes has changed in the past decade, driven mainly by the development of new materials that open the possibility of manufacturing electrodes with adaptable mechanical properties and promising electrical properties. In this paper, we report on the mechanical and electrochemical properties of a polydimethylsiloxane (PDMS) composite with edge-functionalized graphene (EFG) and demonstrate its potential for use in neural implants with the fabrication of a novel neural cuff electrode. We have shown that a 200 µm thick 1:1 EFG/PDMS composite film has a stretchability of up to 20%, a Young's modulus of 2.52 MPa, and a lifetime of more than 10000 mechanical cycles, making it highly suitable for interfacing with soft tissue. Electrochemical characterization of the EFG/PDMS composite film showed that the capacitance of the composite increased up to 35 times after electrochemical reduction, widening the electrochemical water window and remaining stable after soaking for 5 weeks in phosphate buffered saline. The electrochemically activated EFG/PDMS electrode had a 3 times increase in the charge injection capacity, which is more than double that of a commercial platinum-based neural cuff. Electrochemical and spectrochemical investigations supported the conclusion that this effect originated from the stable chemisorption of hydrogen on the graphene surface. The biocompatibility of the composite was confirmed with an in vitro cell culture study using mouse spinal cord cells. Finally, the potential of the EFG/PDMS composite was demonstrated with the fabrication of a novel neural cuff electrode, whose double-layered and open structured design increased the cuff stretchability up to 140%, well beyond that required for an operational neural cuff. In addition, the cuff design offers better integration with neural tissue and simpler nerve fiber installation and locking.

Exohedral Functionalization of Fullerene by Substituents Controlling of Molecular Organization for Spontaneous C60 Dimerization in Liquid Crystal Solutions and in a Bulk Controlled by a Potential.

A study was carried out on the possibility of orderly and spontaneous dimerization at room temperature of C60 cages in fullerene liquid crystal fullerene dyads (R-C60). For this purpose, dyads with a structural elements feature supporting π-stacking and Van der Waals interactions were tested, due to the presence of terthiophene donors linked through an α-position or dodecyloxy chains. In addition, this possibility was also tested and compared to dyads with shorter substituents and the pristine C60. Research has shown that only in dyads with the features of liquid crystals, π-dimerization of C60 units occurs, which was verified by electrochemical and spectroelectrochemical (ESR) measurements. Cyclic voltammetry and differential voltammetry studies reveal π-dimerization in liquid crystal dyad solution even without the possibility of previous polymerization (cathodic or anodic) under conditions in the absence of irradiation and without the availability of reaction initiators, and even with the use of preliminary homogenization. These dyads undergo six sequential, one-electron reductions of π-dimer (R-C60···C60-R), where two electrons are added successively to each of the two fullerene cages and first form two radical anion system (R-C60)•-(R-C60)•- without pairing with the characteristics of two doublets. Similarly, the second reductions of π-dimer occur at potentials that are close to the reduction potential for the conversion to a system of two triplet dianions (R-C60)2-(R-C60)2-. Electron paramagnetic resonance spectra indicate a significant interaction between C60 cages. Interestingly, the strength of intermolecular bonds is so significant that it can overcome Coulombic repulsion, even with such highly charged particles as dianions and trianions. Such behavior has been revealed and studied so far only in covalently bonded C60 dimers.

Electrochemical and Spectroelectrochemical Studies on the Reactivity of Perimidine-Carbazole-Thiophene Monomers towards the Formation of Multidimensional Macromolecules versus Stable π-Dimeric States.

During research on cross-linked conducting polymers, double-functionalized monomers were synthesized. Two subunits potentially able to undergo oxidative coupling were used-perimidine and, respectively, carbazole, 3,6-di(hexylthiophene)carbazole or 3,6-di(decyloxythiophene)carbazole; alkyl and alkoxy chains as groups supporting molecular ordering and 14H-benzo[4,5]isoquinone[2,1-a]perimidin-14-one segment promoting CH⋯O interactions and π-π stacking. Electrochemical, spectroelectrochemical, and density functional theory (DFT) studies have shown that potential-controlled oxidation enables polarization of a specific monomer subunit, thus allowing for simultaneous coupling via perimidine and/or carbazole, but mainly leading to dimer formation. The reason for this was the considerable stability of the dicationic and tetracationic π-dimers over covalent bonding. In the case of perimidine-3,6-di(hexylthiophene)carbazole, the polymer was not obtained due to the steric hindrance of the alkyl substituents preventing the coupling of the monomer radical cations. The only linear π-conjugated polymer was obtained through di(decyloxythiophene)carbazole segment from perimidine-di(decyloxythiophene)-carbazole precursor. Due to the significant difference in potentials between subsequent oxidation states of monomer, it was impossible to polarize the entire molecule, so that both directions of coupling could be equally favored. Subsequent oxidation of this polymer to polarize the side perimidine groups did not allow further crosslinking, because rather the π-π interactions between these perimidine segments dominate in the solid product.

Amphiphilic Zinc Porphyrin Single-Walled Carbon Nanotube Hybrids: Efficient Formation and Excited State Charge Transfer Studies.

Herein, the microscopic and spectroscopic characterization of a novel non-covalent electron donor-acceptor system, in which three different metalloporphyrins (1, 2, and 3) play the dual role of light harvester and electron donor with SWCNTs as electron acceptor, is described. To this end, microscopy, that is, atomic force microscopy (AFM) and transmission electron microscopy (TEM) corroborate the formation of 1-SWCNT, 2-SWCNT, and 3-SWCNT. Spectroscopy by means of Raman, fluorescence, and transient absorption spectroscopy confirmed efficient charge-transfer interaction from photoexcited metalloporphyrins to SWCNTs in the ground and excited state of 1-SWCNT, 2-SWCNT, and 3-SWCNT. The complementary use of spectroelectrochemical and transient absorption measurements substantiates the formation of one-electron oxidized metalloporphyrins after photoexcitation. Multiwavelength global analysis provides insights into the charge-separation and recombination processes in 1-SWCNT, 2-SWCNT, and 3-SWCNT upon photoexcitation. Notably, both the charge-separation and recombination dynamics are fastest in 2-SWCNT. Importantly, the strongest interactions in the steady-state experiments are associated with the fastest excited state decay in the time-resolved measurements.

Investigation of Ferrocene Linkers in ß-Substituted Porphyrins.

A series of ß-ferrocene-modified zinc porphyrins, with various electron-withdrawing units appended to the ferrocene, were synthesized, and their electronic properties were investigated. The ferrocene was able to be modified with the substituents, with its oxidation potential increased by up to 0.3 V, without significantly perturbing the porphyrin core. A small red-shift of the strongest absorption band (B band) occurred upon the addition of the electron-withdrawing substituents (270 cm-1), occurring alongside a broadening of the band. The singlet state is unaffected by the ferrocene substitution; however, the triplet state lifetimes are decreased by 10.4-10.6 µs from that of the unsubstituted ferrocene porphyrin (18.1 µs). Computational studies showed that the changes in the optical properties are due to a loss of degeneracy of the porphyrin lowest unoccupied molecular orbitals; this is supported by resonance Raman spectroscopy studies, which show different enhancement patterns when probing the high- and low-energy edges of the B band.

Optimizing Electron Densities of Ni-N-C Complexes by Hybrid Coordination for Efficient Electrocatalytic CO2 Reduction.

Metal-N-C is a type of attractive electrocatalyst for efficient CO2 reduction to CO. Because of the ambiguity in their atomic structures, the active sites and catalytic mechanisms of the catalysts have remained under debate. Here, the effects of N and C hybrid coordination on the activity of Ni-N-C catalysts were investigated, combining theoretical and experimental methods. The theoretical calculations revealed that N and C hybrid coordination greatly enhanced the capability of single-atom Ni active sites to provide electrons to reactant molecules and strengthens the bonding of Ni to N and C in the Ni-N-C complexes. During the reaction process, the C and N coordination synergistically optimized the reaction energies in the conversion of CO2 to CO. A good agreement between theoretical calculations and electrochemical experiments was achieved based on the newly developed Ni-N-C electrocatalysts. The activity of hybrid-coordination NiN2 C2 was more than double that of single-coordination NiN4 .

Self-Healing Electrode with High Electrical Conductivity and Mechanical Strength for Artificial Electronic Skin.

A self-healing electrode is an electrical conductor that can repair internal damage by itself, similar to human skin. Since self-healing electrodes are based on polymers and hydrogels, these components are still limited by low electrical conductivity and mechanical strength. In this study, we designed an electrically conductive, mechanically strong, and printable self-healing electrode using liquid crystal graphene oxide (LCGO) and silver nanowires (AgNWs). The conductive ink was easily prepared by simply mixing LCGO and AgNWs solutions. The ultrathin (3 µm thick) electrode can be printed in various shapes, such as a butterfly, in a freestanding state. The maximum conductivity and strength of the LCGO/AgNW composite were 17 800 S/cm and 4.2 MPa, respectively; these values are 24 and 4 times higher, respectively, than those of a previously developed self-healing electrode. The LCGO/AgNW composite self-healed internal damage in ambient conditions with moisture and consequently recovered 96.8% electrical conductivity and 95% mechanical toughness compared with the undamaged state. The electrical properties of the composite exhibited metallic tendencies. Therefore, these results suggest that the composite can be used as an artificial electronic skin that detects environmental conditions, such as compression and temperature. This self-healing artificial electronic skin could be applied to human condition monitoring and robotic sensing systems.

Dual Droplet Functionality: Phototaxis and Photopolymerization.

The use of phototaxis to move droplets in liquids offers the opportunity to emulate natural processes such as the controlled transport of materials in fluidic environments and to undertake chemistry at specific locations. We have developed a photoactive organic droplet, whose movement in aqueous solution is driven by a photoinitiator, as a result of a light-induced reaction within the droplet generating a Marangoni flow. The photoinitiator not only drives the droplet motion but can also be used to initiate polymerization following transfer of the droplet to a specific location and its merging with a monomer-containing droplet. The same light is used to control the transport of the droplet and the polymerization. The efficacy of this droplet transport and reactor system has been demonstrated by the site-specific underwater polymerization of N-isopropylacrylamide to repair a leaking vessel and the adhesion of two materials together.

Bio-Inspired Stretchable and Contractible Tough Fiber by the Hybridization of GO/MWNT/Polyurethane.

Spider silks represent stretchable and contractible fibers with high toughness. Those tough fibers with stretchability and contractibility are attractive as energy absorption materials, and they are needed for wearable applications, artificial muscles, and soft robotics. Although carbon-based materials and poly(vinyl alcohol) (PVA) composite fibers exhibit high toughness, they are still limited in low extensibility and an inability to operate in the wet-state condition. Herein, we report stretchable and contractible fiber with toughness that is inspired by the structure of spider silk. The bioinspired tough fiber provides 495 J/g of gravimetric toughness, which exceeds 165 J/g of spider silk. Besides, the tough fiber was reversibly stretched to ∼80% strain without damage. This toughness and stretchability are realized by hybridization of aligned graphene oxide/multiwalled carbon nanotubes in a polyurethane matrix as elastic amorphous regions and ß-sheet segments of spider silk. Interestingly, the bioinspired tough fiber contracted up to 60% in response to water and humidity similar to supercontraction of the spider silk. It exhibited 610 kJ/m3 of contractile energy density, which is higher than previously reported moisture driven actuators. Therefore, this stretchable and contractible tough fiber could be utilized as an artificial muscle in soft robotics and wearable devices.

When "Donor-Acceptor" Dyes Delocalize: A Spectroscopic and Computational Study of D-A Dyes Using "Michler's Base".

In this study, we show that the "Michler's base" motif can be combined in a donor-acceptor arrangement with a range of acceptor units (indandione, indandione with cyano substituents, barbituric acid, or rhodanine) to give photophysical properties that are dominated by delocalized excited states. By changing the acceptor unit and by altering the planarity of this system, it is possible to tune the low-energy absorption feature in terms of intensity from 23 000 to 67 000 M-1 cm-1 and energy between 500 and 700 nm. Resonance Raman spectroscopy and time-dependent density functional theory indicate that this absorption feature has two underlying transitions: a weaker charge-transfer transition around 500 nm and a strong mixed or delocalized transition between 550 and 700 nm. Generally, these compounds are not strongly emissive; however, dual emission is observed, and the relative intensity of the two states can be modulated by solvent polarity. The energy of these emissive states does not correlate with the Lippert-Mataga analysis in which the Stokes shift is related to the solvent polarity (Δf).

Publisher Correction: Room temperature CO2 reduction to solid carbon species on liquid metals featuring atomically thin ceria interfaces.

The original version of this Article contained errors in the author affiliations. Affiliation 1 incorrectly read 'School of Chemical Engineering, University of New South Wales (UNSW), Sydney, NSW 2031, Australia' and affiliation 4 incorrectly read 'School of Engineering, RMIT University, Melbourne, VIC 3001, Australia.' This has now been corrected in both the PDF and HTML versions of the Article.

Room temperature CO2 reduction to solid carbon species on liquid metals featuring atomically thin ceria interfaces.

Negative carbon emission technologies are critical for ensuring a future stable climate. However, the gaseous state of CO2 does render the indefinite storage of this greenhouse gas challenging. Herein, we created a liquid metal electrocatalyst that contains metallic elemental cerium nanoparticles, which facilitates the electrochemical reduction of CO2 to layered solid carbonaceous species, at a low onset potential of -310 mV vs CO2/C. We exploited the formation of a cerium oxide catalyst at the liquid metal/electrolyte interface, which together with cerium nanoparticles, promoted the room temperature reduction of CO2. Due to the inhibition of van der Waals adhesion at the liquid interface, the electrode was remarkably resistant to deactivation via coking caused by solid carbonaceous species. The as-produced solid carbonaceous materials could be utilised for the fabrication of high-performance capacitor electrodes. Overall, this liquid metal enabled electrocatalytic process at room temperature may result in a viable negative emission technology.

Silicon as a ubiquitous contaminant in graphene derivatives with significant impact on device performance.

Silicon-based impurities are ubiquitous in natural graphite. However, their role as a contaminant in exfoliated graphene and their influence on devices have been overlooked. Herein atomic resolution microscopy is used to highlight the existence of silicon-based contamination on various solution-processed graphene. We found these impurities are extremely persistent and thus utilising high purity graphite as a precursor is the only route to produce silicon-free graphene. These impurities are found to hamper the effective utilisation of graphene in whereby surface area is of paramount importance. When non-contaminated graphene is used to fabricate supercapacitor microelectrodes, a capacitance value closest to the predicted theoretical capacitance for graphene is obtained. We also demonstrate a versatile humidity sensor made from pure graphene oxide which achieves the highest sensitivity and the lowest limit of detection ever reported. Our findings constitute a vital milestone to achieve commercially viable and high performance graphene-based devices.

Efficient and Stable Solid-State Dye-Sensitized Solar Cells by the Combination of Phosphonium Organic Ionic Plastic Crystals with Silica.

Remarkably efficient quasi-solid-state dye-sensitized solar cells (DSSCs) have been fabricated using organic ionic plastic crystal electrolytes based on a small triethyl(methyl)phosphonium [P1222] cation and two types of sulfonamide anions, bis(fluorosulfonyl)amide (FSA) and bis(trifluoromethanesulfonyl)amide (TFSA), in combination with varying amounts of silica (SiO2). Solar cell efficiencies of up to 7.4% were obtained, which is comparable to our benchmark efficiencies of liquid (acetonitrile) electrolyte-based devices. Such a high efficiency for DSSCs using quasi-solid-state electrolytes is attributed to improved ionic conductivity, enhanced redox couple transport, improved interfacial interaction between the electrolyte and the electrode as well as decreased resistance at both electrode interfaces. Notably, the devices with the silica-containing electrolytes displayed excellent stability after 5 months of storage, with the most stable devices, formed with either plastic crystal electrolyte containing 2% silica, showing no decrease in efficiency.

Moving Droplets in 3D Using Light.

The emulation of the complex cellular and bacterial vesicles used to transport materials through fluids has the potential to add revolutionary capabilities to fluidic platforms. Although a number of artificial motile vesicles or microdroplets have been demonstrated previously, control over their movement in liquid in 3D has not been achieved. Here it is shown that by adding a chemical "fuel," a photoactive material, to the droplet, it can be moved in any direction (3D) in water using simple light sources without the need for additives in the water. The droplets can be made up of a range of solvents and move with speeds as high as 10.4 mm s-1 toward or away from the irradiation source as a result of a light-induced isothermal change in interfacial tension (Marangoni flow). It is further demonstrated that more complex functions can be accomplished by merging a photoactive droplet with a droplet carrying a "cargo" and moving the new larger droplet to a "reactor" droplet where the cargo undergoes a chemical reaction. The control and versatility of this light-activated, motile droplet system will open up new possibilities for fluidic chemical transport and applications.

Computational and Spectroscopic Analysis of ß-Indandione Modified Zinc Porphyrins.

Porphyrins have characteristic optical properties which give them the potential to be used in a range of applications. In this study, a series of ß-indandione modified zinc porphyrins, systematically changed in terms of linker length and substituent, resulted in absorption spectra that are dramatically different than that observed for the parent zinc porphyrin (ZnTXP, 5,10,15,20-tetrakis(3,5-dimethylphenyl)porphyrinato zinc(II)). These changes include strong absorptions at 420, 541, and 681 nm (110.2, 57.5, and 29.2 mM-1 cm-1, respectively) for the most perturbed compound. Computational studies were conducted and showed the different optical effects are due to a reorganization of molecular orbitals (MOs) away from Gouterman's four-orbital model. The substituent effects alter both unoccupied and occupied MOs. An increased length of linker group raised the energy of the HOMO-2 such that it plays a significant role in the observed transitions. The degenerate LUMO (eg) set are split by substitution, and this splitting may be increased by use of a propylidenodinitrile group, which shows the lowest-energy transitions and the greatest spectral perturbation from the parent zinc porphyrin complex. These data are supported by resonance Raman spectroscopy studies which show distinct enhancement of phenyl modes for high-energy transitions and indandione modes for lower-energy transitions.

Modulation of Donor-Acceptor Distance in a Series of Carbazole Push-Pull Dyes; A Spectroscopic and Computational Study.

A series of eight carbazole-cyanoacrylate based donor-acceptor dyes were studied. Within the series the influence of modifying the thiophene bridge, linking donor and acceptor and a change in the nature of the acceptor, from acid to ester, was explored. In this joint experimental and computational study we have used electronic absorbance and emission spectroscopies, Raman spectroscopy and computational modeling (density functional theory). From these studies it was found that extending the bridge length allowed the lowest energy transition to be systematically red shifted by 0.12 eV, allowing for limited tuning of the absorption of dyes using this structural motif. Using the aforementioned techniques we demonstrate that this transition is charge transfer in nature. Furthermore, the extent of charge transfer between donor and acceptor decreases with increasing bridge length and the bridge plays a smaller role in electronically mixing with the acceptor as it is extended.

Application of terpyridyl ligands to tune the optical and electrochemical properties of a conducting polymer.

We present a simple and effective way of using metal and metal-ligand modifications to tune the electrochemical and optical properties of conducting polymers. To that end, a polyterthiophene functionalized with terpyridine moieties was synthesized and then the resulting film's surface or bulk was modified with different metal ions, namely Fe2+, Zn2+ and Cu2+ and terpyridine. The modification of the terpyridine functionalized polyterthiophene film by Fe2+ increased the absorptivity and electrochemical capacitance of the conducting polymer, and improved its conjugation. Further modification by Zn2+ and Cu2+ resulted in dramatically different spectroelectrochemical properties of the film. Moreover, the influence of the solvents (ACN and 1 : 1 ACN : H2O) in conjunction with the metal ion applied for the modification was found crucial for the electrochemical and optical properties of the films.