The use of flowing
electrochemical reactors, for example, in redox flow batteries and
in various electrosynthesis processes, is increasing. This technology
has the potential to be of central significance in the increased deployment
of renewable electricity for carbon-neutral processes. A key element
of optimizing efficiency of electrochemical reactors is the combination
of high solution conductivity and reagent solubility. Here, we show
a substantial rate of charge transfer for an electrochemical reaction
occurring in a microemulsion containing electroactive material is
loaded inside the nonpolar (toluene) subphase of the microemulsion.
The measured rate constant translates to an exchange current density
comparable to that in redox flow batteries. The rate could be controlled
by the surfactant, which maintains partitioning of reactants and products
by forming an interfacial region with ions in the aqueous phase in
close proximity. The hypothesized mechanism is evocative of membrane-bound
enzymatic reactions. Achieving sufficient rates of electrochemical
reaction is the product of an effort designed to establish a reaction
condition that meets the requirements of electrochemical reactors
using microemulsions to realize a separation of conducting and reactive
elements of the solution, opening a door to the broad use of microemulsions
to effect controlled electrochemical reactions as steps in more complex
processes.
Detection techniques for neurotransmitters that are rapid, label-free, and non-invasive are needed to move towards earlier diagnosis of neurological disease.
In this work, we studied enzyme-catalyzed oxidation of single-walled carbon nanotubes (SWCNTs) produced by the high-pressure carbon monoxide (HiPco) method. While oxidation via strong acids introduced defects sites on SWCNTs and suppressed their near-infrared (NIR) fluorescence, our results indicated that the fluorescence of SWCNTs was restored upon enzymatic oxidation, which provided new evidence that the reaction catalyzed by horseradish peroxidase (HRP) in the presence of H2O2 is mainly a defect-consuming step. These results were further supported by both UV-vis-NIR and Raman spectroscopy. Therefore, employing acid oxidation followed by HRP-catalyzed enzyme oxidation, shortened (< 300 nm in length) and NIR-fluorescent SWCNTs were produced. In contrast, when treated with myeloperoxidase (MPO), H2O2, and NaCl, the oxidized HiPco SWCNTs underwent complete oxidation (i.e. degradation). The shortened, NIR-fluorescent SWCNTs resulting from HRP-catalyzed oxidation of acid cut HiPco SWCNTs may find applications in cellular NIR imaging and drug delivery systems.
Redox flow batteries (RFBs) possess multiple advantages as a flexible energy storage solution. However, RFB researchers are still facing many challenges in finding an appropriate electrolyte. Microemulsions have recently been proposed as a promising alternative RFB electrolyte because of their ability to accommodate organic redox species with fast electron transfer rates that are not soluble in aqueous phase, while still offering the high conductivity of an aqueous salt electrolyte. In this work, we focused on understanding the transport of ferrocene (Fc) in a toluene/Tween 20/1-butanol/water model microemulsion and studied the compositional influence on Fc diffusion. The results show that Fc redistributes among the oil, surfactant, and water microenvironments, and the corresponding diffusion and partition coefficients are quantified. Thus, a tortuous path diffusion model is proposed to describe the mass transport of Fc to an electrode surface. Diffusion coefficients are also obtained by pulsed-field gradient nuclear magnetic resonance (PFG NMR), while the values for Fc diffusion are substantially higher than those from electrochemical measurements, suggesting that they measure samples in different ways. The current contributions from each microenvironment indicate that the Fc permeability is much higher in the oil, even though the electron transfer reaction is likely occurring in the surfactant.
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