Electrochemistry in Micelles and Microemulsions

Rusling, James F.

doi:10.1002/9783527610426.bard020404

Cited by 10 publications

(13 citation statements)

References 47 publications

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“…While much details of structure remain elusive, this provides a definitive indication that a bicontinuous phase is present in contrast to the correlations often used to indicate microemulsion phase structure such as that in Figure b. Taken together, we believe that the neutron results nicely and qualitatively confirm some of the conjectures regarding structure of the microemulsions mentioned in previous studies of electrochemical behavior. − ,− …”

Section: Resultssupporting

confidence: 79%

“…Microemulsions are widely used in a large array of chemical and biochemical systems including a class of polymer synthesis reactions and food and drug formulations. , In addition to possible uses for microemulsions in various synthetic electrochemical processes, microemulsions are of interest in electrochemical reactors since the electrochemistry in such a surfactant-separated system is, broadly speaking, similar to electron transfer processes in biological systems such as biomembranes and, at the more local level, enzymes (mixed polar/nonpolar zones). − Providing for ionic conduction in a separate subphase from that containing the electroactive moiety could lead to broader options for electrochemical reactions.…”

Section: Introductionmentioning

confidence: 99%

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Electron Transfer in Microemulsion-Based Electrolytes

Peng

Cantillo

Nelms

et al. 2020

ACS Appl. Mater. Interfaces

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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.

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Section: Resultssupporting

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Electron Transfer in Microemulsion-Based Electrolytes

Peng

Cantillo

Nelms

et al. 2020

ACS Appl. Mater. Interfaces

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“…This has the effect of making the oxidation process more difficult as the degree of aggregation increases, with E mid = ( E p Ox + E p Red ) varying by 18.2 mV/decade. This is in agreement with literature studies on the influence of self-assembly on redox properties. − Accordingly, we suggest this reflects the additional energy required to separate aggregated molecules, owing to both the increased charge and the “butterfly-shaped”-to-planar transition that occurs on oxidation, which is manifested through an intrinsic activation barrier . Given that ring inversion in dilute solutions of chlorpromazine is considered to be rapid, even at low temperature, , we thus suggest that these data are consistent with conformational change occurring in concert with electron transfer.…”

Section: Resultssupporting

confidence: 92%

Electrochemically Induced Mesomorphism Switching in a Chlorpromazine Hydrochloride Lyotropic Liquid Crystal

et al. 2021

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The discovery of electrochemical switching of the Lα phase of chlorpromazine hydrochloride in water is reported. The phase is characterized using polarizing microscopy, X-ray scattering, rheological measurements, and microelectrode voltammetry. Fast, heterogeneous oxidation of the lyotropic liquid crystal is shown to cause a phase change resulting from the disordering of the structural order in a stepwise process. The underlying molecular dynamics is considered to be a cooperative effect of both increasing electrostatic interactions and an unfolding of the monomers from “butterfly”-shaped in the reduced form to planar in the oxidized form.

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“…Even on repeated use of this exposed electrode, the response continues to present a CV with currents lower than that at a bare GC electrode. It may be recalled that adsorbed layers of surfactants influence the rates of electrochemical reactions as in the case of hemi-micelles on the electrode surface [26,27]. In these systems, an aqueous solution of surfactants above a critical concentration constitutes a complex mobile-phase modifier.…”

Section: Resultsmentioning

confidence: 99%