Combining rotary wet-spinning biofabrication and electro-mechanical stimulation for thein vitroproduction of functional myo-substitutes.

In this work, we present an innovative, high-throughput rotary wet-spinning biofabrication method for manufacturing cellularized constructs composed of highly-aligned hydrogel fibers. The platform is supported by an innovative microfluidic printing head (MPH) bearing a crosslinking bath microtank with a co-axial nozzle placed at the bottom of it for the immediate gelation of extruded core/shell fibers. After a thorough characterization and optimization of the new MPH and the fiber deposition parameters, we demonstrate the suitability of the proposed system for thein vitroengineering of functional myo-substitutes. The samples produced through the described approach were first characterizedin vitroand then used as a substrate to ascertain the effects of electro-mechanical stimulation on myogenic maturation. Of note, we found a characteristic gene expression modulation of fast (MyH1), intermediate (MyH2), and slow (MyH7) twitching myosin heavy chain isoforms, depending on the applied stimulation protocol. This feature should be further investigated in the future to biofabricate engineered myo-substitutes with specific functionalities.

Molecular Precursor Routes for Ag-Based Metallic, Intermetallic, and Metal Sulfide Nanoparticles: Their Comparative ORR Activity Trend at Solid|Liquid and Liquid|Liquid Interfaces.

The electrochemical conversion of oxygen to water is a crucial process required for renewable energy production, whereas its first two-electron step produces a versatile chemical and oxidant─hydrogen peroxide. Improving performance and widening the limited selection of the potential catalysts for this reaction is a step toward the implementation of clean-energy technologies. As silver is known as one of the most effective catalysts of oxygen reduction reaction (ORR), we have designed a suitable molecular precursor pathway for the selective synthesis of metallic (Ag), intermetallic (Ag3Sb), and binary or ternary metal sulfide (Ag2S and AgSbS2) nanomaterials by judicious control of reaction conditions. The decomposition of xanthate precursors under different reaction conditions in colloidal synthesis indicates that carbon-sulfur bond cleavage yields the respective metal sulfide nanomaterials. This is not the case in the presence of trioctylphosphine when the metal-sulfur bond is broken. The synthesized nanomaterials were applied as catalysts of oxygen reduction at the liquid-liquid and solid-liquid interfaces. Ag exhibits the best performance for electrochemical oxygen reduction, whereas the electrocatalytic performance of Ag and Ag3Sb is comparable for peroxide reduction in an alkaline medium. Scanning electrochemical microscopy (SECM) analysis indicates that a flexible 2-electron to 4-electron ORR pathway has been achieved by transforming metallic Ag into intermetallic Ag3Sb.

Tuning composition of CuCo2S4-NiCo2S4 solid solutions via solvent-less pyrolysis of molecular precursors for efficient supercapacitance and water splitting.

Mixed metal sulfides are increasingly being investigated because of their prospective applications for electrochemical energy storage and conversion. Their high electronic conductivity and high density of redox sites result in significant improvement of their electrochemical properties. Herein, the composition-dependent supercapacitive and water splitting performance of a series of Ni(1-x)Cu x Co2S4 (0.2 ≤ x ≤ 0.8) solid solutions prepared via solvent-less pyrolysis of a mixture of respective metal ethyl xanthate precursors is reported. The use of xanthate precursors resulted in the formation of surface clean nanomaterials at low-temperature. Their structural, compositional, and morphological features were examined by p-XRD, SEM, and EDX analyses. Both supercapacitive and electrocatalytic (HER, OER) properties of the synthesized materials significantly vary with composition (Ni/Cu molar content). However, the optimal composition depends on the application. The highest specific capacitance of 770 F g-1 at a current density of 1 A g-1 was achieved for Ni0.6Cu0.4Co2S4 (NCCS-2). This electrode exhibits capacitance retention (C R) of 67% at 30 A g-1, which is higher than that observed for pristine NiCo2S4 (838 F g-1 at 1 A g-1, 47% C R at 30 A g-1). On the contrary, Ni0.4Cu0.6Co2S4 (NCCS-3) exhibits the lowest overpotential of 124 mV to deliver a current density of 10 mA cm-2. Finally, the best OER activity with an overpotential of 268 mV at 10 mA cm-2 was displayed by Ni0.8Cu0.2Co2S4 (NCCS-1). The prepared electrodes exhibit high stability, as well as durability.

Colloidal synthesis of metal chalcogenide nanomaterials from metal-organic precursors and capping ligand effect on electrocatalytic performance: progress, challenges and future perspectives.

Renewable and sustainable functional nanomaterials, which can be employed in alternative green energy sources, are highly desirable. Transition metal chalcogenides are potential catalysts for processes resulting in energy generation and storage. In order to optimize their catalytic performance, high phase purity and precise control over shape and size are indispensable. Metal-organic precursors with pre-formed bonds between the metal and the chalcogenide atoms are advantageous in synthesizing phase pure transition metal chalcogenides with controlled shape and sizes. This can be achieved by the decomposition of metal-organic precursors in the presence of suitable surfactants/capping agents. However, the recent studies on electrocatalysis at the nanoscale level reveal that the capping agents attached to their surface have a detrimental effect on their efficiency. The removal of surfactants from active sites to obtain bare surface nanoparticles is necessary to enhance catalytic activity. Herein, we have discussed the properties of different metal-organic precursors and the role of surfactants in the colloidal synthesis of metal chalcogenide nanomaterials. Moreover, the effect of surfactants on their electrocatalytic performance, the commonly used strategies for removing surfactants from the surface of nanomaterials and the future perspectives are reviewed.

The Solvent Effect on H2 O2 Generation at Room Temperature Ionic Liquid|Water Interface.

H2 O2 is a versatile chemical and can be generated by the oxygen reduction reaction (ORR) in proton donor solution in molecular solvents or room temperature ionic liquids (IL). We investigated this reaction at interfaces formed by eleven hydrophobic ILs and acidic aqueous solution as a proton source with decamethylferrocene (DMFc) as an electron donor. H2 O2 is generated in colorimetrically detectable amounts in biphasic systems formed by alkyl imidazolium hexafluorophosphate or tetraalkylammonium bis(trifluoromethylsulfonyl)imide ionic liquids. H2 O2 fluxes were estimated close to liquid|liquid interface by scanning electrochemical microscopy (SECM). Contrary to the interfaces formed by hydrophobic electrolyte solution in a molecular solvent, H2 O2 generation is followed by cation expulsion to the aqueous phase. Weak correlation between the H2 O2 flux and the difference between DMFc/DMFc+ redox potential and 2 electron ORR standard potential indicates kinetic control of the reaction.

Noble Metal Nanoparticles in Pectin Matrix. Preparation, Film Formation, Property Analysis, and Application in Electrocatalysis.

Stable polymeric materials with embedded nano-objects, retaining their specific properties, are indispensable for the development of nanotechnology. Here, a method to obtain Pt, Pd, Au, and Ag nanoparticles (ca. 10 nm, independent of the metal) by the reduction of their ions in pectin, in the absence of additional reducing agents, is described. Specific interactions between the pectin functional groups and nanoparticles were detected, and they depend on the metal. Bundles and protruding nanoparticles are present on the surface of nanoparticles/pectin films. These films, deposited on the electrode surface, exhibit electrochemical response, characteristic for a given metal. Their electrocatalytic activity toward the oxidation of a few exemplary organic molecules was demonstrated. In particular, a synergetic effect of simultaneously prepared Au and Pt nanoparticles in pectin films on glucose electro-oxidation was found.

Patterning Cu nanostructures tailored for CO2 reduction to electrooxidizable fuels and oxygen reduction in alkaline media.

Due to the limited availability of noble metal catalysts, such as platinum, palladium, or gold, their substitution by more abundant elements is highly advisable. Considerably challenging is the controlled and reproducible synthesis of stable non-noble metallic nanostructures with accessible active sites. Here, we report a method of preparation of bare (ligand-free) Cu nanostructures from polycrystalline metal in a controlled manner. This procedure relies on heterogeneous localized electrorefining of polycrystalline Cu on indium tin oxide (ITO) and glassy carbon as model supports using scanning electrochemical microscopy (SECM). The morphology of nanostructures and thus their catalytic properties are tunable by adjusting the electrorefining parameters, i.e., the electrodeposition voltage, the translation rate of the metal source and the composition of the supporting electrolyte. The activity of the obtained materials towards the carbon dioxide reduction reaction (CO2RR), oxygen reduction reaction (ORR) in alkaline media and hydrogen evolution reaction (HER), is studied by feedback mode SECM. Spiky Cu nanostructures obtained at a high concentration of chloride ions exhibit enhanced electrocatalytic activity. Nanostructures deposited under high cathodic overpotentials possess a high surface-to-volume ratio with a large number of catalytic sites active towards the reversible CO2RR and ORR. The CO2RR yields easily electrooxidizable compounds - formic acid and carbon monoxide. The HER seems to occur efficiently at the crystallographic facets of Cu nanostructures electrodeposited under mild polarization.

Boosting water oxidation layer-by-layer.

Electrocatalysis of water oxidation was achieved using fluorinated tin oxide (FTO) electrodes modified with layer-by-layer deposited films consisting of bilayers of negatively charged citrate-stabilized IrO2 NPs and positively charged poly(diallyldimethylammonium chloride) (PDDA) polymer. The IrO2 NP surface coverage can be fine-tuned by controlling the number of bilayers. The IrO2 NP films were amorphous, with the NPs therein being well-dispersed and retaining their as-synthesized shape and sizes. UV/vis spectroscopic and spectro-electrochemical studies confirmed that the total surface coverage and electrochemically addressable surface coverage of IrO2 NPs increased linearly with the number of bilayers up to 10 bilayers. The voltammetry of the modified electrode was that of hydrous iridium oxide films (HIROFs) with an observed super-Nernstian pH response of the Ir(III)/Ir(IV) and Ir(IV)-Ir(IV)/Ir(IV)-Ir(V) redox transitions and Nernstian shift of the oxygen evolution onset potential. The overpotential of the oxygen evolution reaction (OER) was essentially pH independent, varying only from 0.22 V to 0.28 V (at a current density of 0.1 mA cm(-2)), moving from acidic to alkaline conditions. Bulk electrolysis experiments revealed that the IrO2/PDDA films were stable and adherent under acidic and neutral conditions but degraded in alkaline solutions. Oxygen was evolved with Faradaic efficiencies approaching 100% under acidic (pH 1) and neutral (pH 7) conditions, and 88% in alkaline solutions (pH 13). This layer-by-layer approach forms the basis of future large-scale OER electrode development using ink-jet printing technology.

Synthesis and characterization of porous carbon-MoS2 nanohybrid materials: electrocatalytic performance towards selected biomolecules.

Porous carbon nanohybrids are promising materials as high-performance electrodes for both sensing and energy conversion applications. This is mainly due to their high specific surface area and specific physicochemical properties. Here, new porous nanohybrid materials are developed based on exfoliated MoS2 nanopetals and either negatively charged phenylsulfonated carbon nanoparticles or positively charged sulfonamide functionalized carbon nanoparticles. MoS2 nanopetals not only act as a scaffold for carbon nanoparticles to form 3D porous hierarchical architectures but also result in well-separated electrochemical signals for different compounds. The characteristics of the new carbon nanohybrid materials are studied by dynamic light scattering, zeta potential analysis, high resolution X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy, infrared spectroscopy and electrochemistry. The new hybrid materials show superior charge transport capability and electrocatalytic activity toward selected biologically relevant compounds compared to earlier reports on porous carbon electrodes.

Voltammetric pH Nanosensor.

Nanoscale pH evaluation is a prerequisite for understanding the processes and phenomena occurring at solid-liquid, liquid-liquid, and liquid-gas interfaces, e.g., heterogeneous catalysis, extraction, partitioning, and corrosion. Research on the homogeneous processes within small volumes such as intracellular fluids, microdroplets, and microfluidic chips also requires nanometer scale pH assessment. Due to the opacity of numerous systems, optical methods are useless and, if applicable, require addition of a pH-sensitive dye. Potentiometric probes suffer from many drawbacks such as potential drift and lack of selectivity. Here, we present a voltammetric nanosensor for reliable pH assessment between pH 2 and 12 with high spatial resolution. It consists of a pyrolytic carbon nanoelectrode obtained by chemical vapor deposition (CVD) inside a quartz nanopipette. The carbon is modified by adsorption of syringaldazine from its ethanolic solution. It exhibits a stable quasi-reversible cyclic voltammogram with nearly Nernstian dependency of midpeak potentials (-54 mV/pH). This sensor was applied as a probe for scanning electrochemical microscopy (SECM) in order to map pH over a platinum ultramicroelectrode (UME), generating hydroxide ions (OH(-)) by the oxygen reduction reaction (ORR) at a diffusion-controlled rate in aerated phosphate buffered saline (PBS). The results reveal the alkalization of the electrolyte close to the oxygen reducing electrode, showing the insufficient buffer capacity of PBS to maintain a stable pH at the given conditions.

Tailored gold nanostructure arrays as catalysts for oxygen reduction in alkaline media and a single molecule SERS platform.

Although plenty of functional nanomaterials are widely applied in science and technology, cost-efficient, controlled and reproducible fabrication of metallic nanostructures is a considerable challenge. Automated electrorefining by scanning electrochemical microscopy (SECM) provides an effective approach to circumvent some drawbacks of traditional homogeneous syntheses of nanoparticles, providing precise control over the amount, time and place of reactant delivery. The precursor is just a raw metal, which is the most economically viable source. This approach ensures reproducibility and the opportunity for fabrication of micropatterns, which can be rapidly analyzed by scanning probe techniques. Here, a cost-effective methodology for the preparation of naked (ligand-free) metallic nanostructures, from polycrystalline gold using a moving microelectrode, is presented. Automated micropatterning of bare gold on indium tin oxide (ITO) demonstrates the versatility of this method to tune the size and shape of the nanostructures. The morphology of the obtained materials and thus their catalytic and plasmonic properties can be tuned using the electrorefining parameters. Programmable fabrication of sample microarrays by microprinting followed by comparative SECM studies or spectroscopic analysis allows quick optimization and characterization for specific purposes. Electrocatalytic oxygen reduction in alkaline media and surface-enhanced Raman spectroscopy (SERS) of single porphycene molecules are presented as model examples.

Catalysis at the room temperature ionic liquid|water interface: H2O2 generation.

H2O2 is produced at the interface between a room-temperature ionic liquid with decamethylferrocene as an electron donor and an acidic aqueous solution. The electron donor can be regenerated electrochemically.

Catalysis of water oxidation in acetonitrile by iridium oxide nanoparticles.

Water oxidation catalysed by iridium oxide nanoparticles (IrO2 NPs) in water-acetonitrile mixtures using [RuIII(bpy)3]3+ as oxidant was studied as a function of the water content, the acidity of the reaction media and the catalyst concentration. It was observed that under acidic conditions (HClO4) and at high water contents (80% (v/v)) the reaction is slow, but its rate increases as the water content decreases, reaching a maximum at approximately equimolar proportions (≈25% H2O (v/v)). The results can be rationalized based on the structure of water in water-acetonitrile mixtures. At high water fractions, water is present in highly hydrogen-bonded arrangements and is less reactive. As the water content decreases, water clustering gives rise to the formation of water-rich micro-domains, and the number of bonded water molecules decreases monotonically. The results presented herein indicate that non-bonded water present in the water micro-domains is considerably more reactive towards oxygen production. Finally, long term electrolysis of water-acetonitrile mixtures containing [RuII(bpy)3]2+ and IrO2 NPs in solution show that the amount of oxygen produced is constant with time demonstrating that the redox mediator is stable under these experimental conditions.

Facile and rapid synthesis of Pd nanodendrites for electrocatalysis and surface-enhanced Raman scattering applications.

Numerous properties from metal nanostructures can be tuned by controlling both their size and shape. In particular, the latter is extremely important because the type of crystalline surface affects the surface electronic density. This paper describes a simple approach to the synthesis of highly-structured, anisotropic palladium nanostructured dendrites. They were obtained using an eco-friendly biomolecule 5-hydroxytryptophan, which acts as both a reducing and stabilizing agent. The growth mechanism is proposed for the evolution of dendrites morphology. It was found that the concentration of 5-hydroxytryptophan played a vital role on the morphology of the nanostructured Pd dendrites. This nanomaterial shows enhanced electrocatalytic performance towards the oxidation of formic acid, and it exhibits surface-enhanced Raman scattering properties towards the prostate specific antigen. These properties may be explored in fuel cells and biosensors, respectively.

Selective electrochemical detection of dopamine in a microfluidic channel on carbon nanoparticulate electrodes.

There is a continuous need for the construction of detection systems in microfluidic devices. In particular, electrochemical detection allows the separation of signals from the analyte and interfering substances in the potential domain. Here, a simple microfluidic device for the sensitive and selective determination of dopamine in the presence of interfering substances was constructed and tested. It employs a carbon nanoparticulate electrode allowing the separation of voltammetric signals of dopamine and common interfering substances (ascorbic acid and acetaminophen) both in quiescent conditions and in flow due to the electrocatalytic effect. These voltammograms were also successfully simulated. The limit of detection of dopamine detected by square wave voltammetry in 1 mM solutions of interfering substances in phosphate buffered saline is about 100 nM. In human serum a clear voltammetric signal could be seen for a 200 nM solution, sufficient to detect dopamine in the cerebral fluid. Flow injection analysis allows a decrease in the limit of detection down to 3.5 nM.

Surprising acidity of hydrated lithium cations in organic solvents.

Lithium cations are shown to have a significant role in catalyzing oxygen and proton reduction along with S(N)1 reactions in biphasic systems. We propose that this catalytic effect is due to the surprising acidity of the hydrated cations; interactions between the cation and its surrounding solvation shell will make the constituent water molecules more acidic.

Functionalized carbon nanoparticles, blacks and soots as electron-transfer building blocks and conduits.

Functionalized carbon nanoparticles (or blacks) have promise as novel active high-surface-area electrode materials, as conduits for electrons to enzymes or connections through lipid films, or as nano-building blocks in electroanalysis. With previous applications of bare nanoblacks and composites mainly in electrochemical charge storage and as substrates in fuel cell devices, the full range of benefits of bare and functionalized carbon nanoparticles in assemblies and composite (bio)electrodes is still emerging. Carbon nanoparticles are readily surface-modified, functionalized, embedded, or assembled into nanostructures, employed in bioelectrochemical systems, and incorporated into novel electrochemical sensing devices. This focus review summarizes aspects of a rapidly growing field and some of the recent developments in carbon nanoparticle functionalization with potential applications in (bio)electrochemical, photoelectrochemical, and electroanalytical processes.

Self-powered biosensor for ascorbic acid with a Prussian blue electrochromic display.

We report on the development of a nanocarbon based anode for sensing of ascorbic acid (AA). The oxidation of AA on this anode occurs at a quite low overpotential which enables the anode to be connected to a biocathode to form an ascorbic acid/O2 biofuel cell that functions as a self-powered biosensor. In conjunction with a Prussian blue electrochromic display the anode can also work as a truly self-powered sensor. The oxidation of ascorbic acid at the anode leads to a reduction of the Prussian blue in the display. The reduced form of Prussian blue, called Prussian white, is transparent. The rate of change from blue to colourless is dependent on the concentration of ascorbic acid. The display can easily be regenerated by connecting it to the biocathode which returns the Prussian blue to its oxidized form. In this way we have created the first self-powered electrochromic sensor that gives quantitative information about the analyte concentration. This is demonstrated by measuring the concentration of ascorbic acid in orange juice. The reported quantitative read-out electrochromic display can serve as a template for the creation of cheap, miniturizable sensors for other relevant analytes.

Anomalous effect of flow rate on the electrochemical behavior at a liquid|liquid interface under microfluidic conditions.

We have investigated the oxidation of ferrocene at a flowing organic solvent|aqueous electrolyte|solid electrode junction in a microfluidic setup using cyclic voltammetry and fluorescent laser scanning confocal microscopy. At low flow rates the oxidation current decreases with increasing flow, contrary to the Levich equation, but at higher flow rates the current increases linearly with the cube root of the flow rate. This behavior is explained using a simple model postulating a smallest effective width of the three-phase junction, which after fitting to the data comes to be ca. 20 µm. The fluorescence microscopy reveals mixing of the two phases close to the PDMS cover, but the liquid|liquid junction is stable close to the glass support. This study shows the importance of the solid|liquid|liquid junctions for the behavior of multiphase systems under microfluidic conditions.