Dramatic Drop in Cell Resistance through Induced Dipoles and Bipolar Electrochemistry

The use of slurries of conducting particles has been considered a way to extend the electrode area in some energy storage electrochemical cells. When suspensions of conducting particles are used in electrolytes a decreased impedance is observed, even for concentrations much lower than the theoretical percolation limits. Indeed, it is known that polarization occurs when a conducting material is immersed in an electrolyte in presence of electric fields, and bipolar electrochemistry processes may occur. This work demonstrates the dramatic drop in resistance for electrochemical cells with just a few macroscopic conducting pieces immersed in the electrolyte, in the absence of any electrical contact, through bipolar induction. Furthermore, mediation of soluble redox species between adjacent induced poles of opposite charge results in an additional mechanism for charge transfer, contributing further to the decrease in impedance. Relevant parameters like size, geometry, and spatial occupation of inducible pieces within the electric field, are relevant. Remarkably, the effects observed can explain some empirical observations previously reported for carbon suspensions and slurries. Thus, no electronic percolation requiring particle contact, nor ordering, are needed to explain the good performance associated to lowered impedance These results suggest new engineering designs for electrochemical cells with enhanced currents

Bromine and Oxygen Redox Species Mediated Highly Selective Electro-Epoxidation of Styrene

The olefin epoxidation is an essential transformation and arouses great interest among the scientific community for the key role of epoxide in the chemical industry. Traditional methods suffer from harmful...

Operando magnetic resonance imaging for mapping of temperature and redox species in thermo-electrochemical cells

Low-grade waste heat is an abundant and underutilised energy source. In this context, thermo-electrochemical cells (i.e., systems able to harvest heat to generate electricity) are being intensively studied to deliver the promises of efficient and cost-effective energy harvesting and electricity generation. However, despite the advances in performance disclosed in recent years, understanding the internal processes occurring within these devices is challenging. In order to shed light on these mechanisms, here we report an operando magnetic resonance imaging approach that can provide quantitative spatial maps of the electrolyte temperature and redox ion concentrations in functioning thermo-electrochemical cells. Time-resolved images are obtained from liquid and gel electrolytes, allowing the observation of the effects of redox reactions and competing mass transfer processes such as thermophoresis and diffusion. We also correlate the physicochemical properties of the system with the device performance via simultaneous electrochemical measurements.

Stimulus-Responsive Smart Nanoparticles-Based CRISPR-Cas Delivery for Therapeutic Genome Editing

The innovative research in genome editing domains such as CRISPR-Cas technology has enabled genetic engineers to manipulate the genomes of living organisms effectively in order to develop the next generation of therapeutic tools. This technique has started the new era of “genome surgery”. Despite these advances, the barriers of CRISPR-Cas9 techniques in clinical applications include efficient delivery of CRISPR/Cas9 and risk of off-target effects. Various types of viral and non-viral vectors are designed to deliver the CRISPR/Cas9 machinery into the desired cell. These methods still suffer difficulties such as immune response, lack of specificity, and efficiency. The extracellular and intracellular environments of cells and tissues differ in pH, redox species, enzyme activity, and light sensitivity. Recently, smart nanoparticles have been synthesized for CRISPR/Cas9 delivery to cells based on endogenous (pH, enzyme, redox specie, ATP) and exogenous (magnetic, ultrasound, temperature, light) stimulus signals. These methodologies can leverage genome editing through biological signals found within disease cells with less off-target effects. Here, we review the recent advances in stimulus-based smart nanoparticles to deliver the CRISPR/Cas9 machinery into the desired cell. This review article will provide extensive information to cautiously utilize smart nanoparticles for basic biomedical applications and therapeutic genome editing.

Electrochemical Performance of Lithographically-Defined Micro-Electrodes for Integration and Device Applications

Small; lithographically-defined and closely-spaced metallic features of dimensions and separation in the micrometer range are of strong interest as working and counter electrodes in compact electrochemical sensing devices. Such micro-electrode systems can be integrated with microfluidics and optical biosensors, such as surface plasmon waveguide biosensors, to enable multi-modal sensing strategies. We investigate lithographically-defined gold and platinum micro-electrodes experimentally, via cyclic voltammetry (CV) measurements obtained at various scan rates and concentrations of potassium ferricyanide as the redox species, in potassium nitrate as the supporting electrolyte. The magnitude of the double-layer capacitance is estimated using the voltammograms. Concentration curves for potassium ferricyanide are extracted from our CV measurements as a function of scan rate, and could be used as calibration curves from which an unknown concentration of potassium ferricyanide in the range of 0.5–5 mM can be determined. A blind test was done to confirm the validity of the calibration curve. The diffusion coefficient of potassium ferricyanide is also extracted from our CV measurements by fitting to the Randles–Sevcik equation (D = 4.18 × 10−10 m2/s). Our CV measurements were compared with measurements obtained using macroscopic commercial electrodes, yielding good agreement and verifying that the shape of our CV curves do not depend on micro-electrode geometry (only on area). We also compare our CV measurements with theoretical curves computed using the Butler–Volmer equation, achieving essentially perfect agreement while extracting the rate constant at zero potential for our redox species (ko = 10−6 m/s). Finally, we demonstrate the importance of burn-in to stabilize electrodes from the effects of electromigration and grain reorganization before use in CV measurements, by comparing with results obtained with as-deposited electrodes. Burn-in (or equivalently, annealing) of lithographic microelectrodes before use is of general importance to electrochemical sensing devices

Investigating chromium cycling in global oxygen deficient zones with chromium isotopes

Chromium (Cr) isotopes have shown great potential as a paleo-redox proxy to trace the redox conditions of ancient oceans and atmosphere. However, its cycling in modern environments is poorly constrained. In my thesis, I attempt to fill in the gap of our understanding of chromium cycling in the modern ocean, with a focus on the redox processes in global oxygen deficient zones (ODZs). Firstly, we developed a method to analyze Cr isotopes of different Cr redox species. Tests on processing conditions demonstrated its robustness in obtaining accurate Cr isotope data. It is applicable to both frozen and fresh samples. This method allows us to investigate the redox cycling of Cr that is hard to unravel by existing total Cr methods. Secondly, in the Eastern Tropical North Pacific (ETNP), Eastern Tropical South Pacific (ETSP) and Arabian Sea ODZs, their total dissolved Cr profiles show preferential reduction of isotopically light Cr(VI) to Cr(III), which is scavenged and exported to deeper oceans. Applying our new method to ETNP and ETSP ODZ seawater samples, we observed Cr(VI) reduction in both ODZs with a similar fractionation factor. This indicates similar mechanisms may be controlling Cr(VI) reduction in the two ODZs. Cr(III) maximum coincides with Fe(II) and secondary nitrite maximums in the upper core of both ODZs. Shipboard incubations with spiked Fe(II) showed fast Cr(VI) reduction occurring in the ETNP ODZ. But neither Fe(II) nor microbes were reducing Cr(VI) directly. Thirdly, we calculated the isotope effects of Cr scavenging in the ETNP and ETSP ODZs. Thetwo ODZs show a similar isotope partitioning during Cr scavenging. And spatial variability is observed in the ETNP ODZ. Our calculated scavenged Cr isotope ratio is lighter than that of the total dissolved Cr from the same depth. It is also comparable to that of reducing or anoxic sediments, which implies that Cr isotopes can be used as an archive for local redox conditions.

Fully Inkjet-Printed Biosensors Fabricated with a Highly Stable Ink Based on Carbon Nanotubes and Enzyme-Functionalized Nanoparticles

Enzyme inks can be inkjet printed to fabricate enzymatic biosensors. However, inks containing enzymes present a low shelf life because enzymes in suspension rapidly lose their catalytic activity. Other major problems of printing these inks are the non-specific adsorption of enzymes onto the chamber walls and stability loss during printing as a result of thermal and/or mechanical stress. It is well known that the catalytic activity can be preserved for significantly longer periods of time and to harsher operational conditions when enzymes are immobilized onto adequate surfaces. Therefore, in this work, horseradish peroxidase was covalently immobilized onto silica nanoparticles. Then, the nanoparticles were mixed into an aqueous ink containing single walled carbon nanotubes. Electrodes printed with this specially formulated ink were characterized, and enzyme electrodes were printed. To test the performance of the enzyme electrodes, a complete amperometric hydrogen peroxide biosensor was fabricated by inkjet printing. The electrochemical response of the printed electrodes was evaluated by cyclic voltammetry in solutions containing redox species, such as hexacyanoferrate (III/II) ions or hydroquinone. The response of the enzyme electrodes was studied for the amperometric determination of hydrogen peroxide. Three months after the ink preparation, the printed enzyme electrodes were found to still exhibit similar sensitivity, demonstrating that catalytic activity is preserved in the proposed ink. Thus, enzyme electrodes can be successfully printed employing highly stable formulation using nanoparticles as carriers.

Operando MRI for quantitative mapping of temperature and redox species concentrations in thermo-electrochemical cells

Low-grade waste heat is an abundant and underutilised energy source, and the promise of thermo-electrochemical cells to harvest this resource and power applications such as wearable devices and sensors is increasingly being realised. However, despite substantial advances in performance in recent years, understanding the interior processes occurring within these devices remains a challenge. Here we report an operando magnetic resonance imaging (MRI) approach that can provide quantitative spatial maps of electrolyte temperature and redox ion concentrations in functioning thermo-electrochemical cells. Time-resolved images are obtained from liquid and gel electrolytes, allowing the effects of redox reactions and competing mass transfer effects such as thermophoresis and diffusion to be visualised and correlated with the device performance via simultaneous electrochemical measurements. This method offers valuable insights into these devices and will greatly aid their future design and optimisation.